Certain 2-(2-substituted benzoyl)-1,3-cyclohexanediones

ABSTRACT

Compounds of the formula ##STR1## wherein R is halogen, C 1  -C 4  alkoxy, C 1  -C 4  alkyl, C 1  -C 4  haloalkyl, cyano, nitro, S(O) n  R wherein R is C 1  -C 4  alkyl and n is the integer 0, 1 or 2; and R 2  through R 8  are hydrogen or certain substituents, their salts, herbicidal compositions containing the compound or salts and the herbicidal use thereof.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a divisional of application Ser. No. 880,370, filed June 30, 1986, now U.S. Pat. No. 4,780,127.

Ser. No. 880,370 is a continuation-in-part application of Ser. No. 772,593, filed Sept. 5, 1985, now abandoned; which in turn is a continuation-in-part application of Ser. No. 634,408, filed July 31, 1984, now abandoned; which in turn is a continuation-in-part application of Ser. No. 587,331, filed Mar. 7, 1984, now abandoned; which in turn is a continuation-inpart of application Ser. No. 532,869, filed Sept. 16, 1983, now abandoned; which in turn is a continuation-in-part application of Ser. No. 464,251, filed Feb. 9, 1983, now abandoned; which in turn is a continuation-in-part application of Ser. No. 361,658, filed Mar. 25, 1982, now abandoned.

Ser. No. 880,370 is also a continuation-in-part of application Ser. No. 752,702, filed July 8, 1985, now abandoned; which in turn is a continuation-in-part application of Ser. No. 640,791, filed Aug. 17, 1984, now abandoned, which in turn is a continuation-in-part application of Ser. No. 566,077, filed Dec. 27, 1983, now abandoned; which in turn is a continuation-in-part of application Ser. No. 532,882, filed Sept. 16, 1983, now abandoned.

Ser. No. 880,370 is also a continuation-in-part of application Ser. No. 804,026, filed Dec. 3, 1985, now abandoned; which in turn is a continuation of application Ser. No. 683,899, filed Dec. 20, 1984, now abandoned.

Ser. No. 880,370 is also a continuation-in-part application of application Ser. No. 802,135, filed Nov. 29, 1985, now abandoned; which in turn is a continuation-in-part of application Ser. No. 683,900, filed Dec. 20, 1984, now abandoned.

Ser. No. 880,370 is a also continuation-in-part application of Ser. No. 802,133, filed Nov. 29, 1985, now abandoned; which in turn is a continuation-in-part application of Ser. No. 683,898, filed Dec. 20, 1984, now abandoned.

Ser. No. 880,370 is also a continuation-in-part application of application Ser. No. 802,134, filed Nov. 29, 1985, now abandoned; which in turn is a continuation-in-part of application Ser. No. 683,884, filed Dec. 20, 1984, now abandoned.

Ser. No. 880,370 is also a continuation-in-part application of Ser. No. 872,067, filed June 9, 1986, now abandoned.

Applicants specifically incorporate by reference the contents of the above listed U.S. patent applications.

BACKGROUND OF THE INVENTION

Compounds having the structural formula ##STR2## wherein X can be alkyl, n can be 0, 1, or 2, and R₁ can be phenyl or substituted phenyl are described in Japanese Patent Application No. 84632-1974 as being intermediates for the preparation of herbicidal compounds of the formula ##STR3## wherein R₁, X, and n are as defined above and R₂ is alkyl, alkenyl, or alkynyl. Specifically taught herbicidal compounds of this latter group are those where n is 2, X is 5,5-dimethyl, R₂ is allyl and R₁ is phenyl, 4-chlorophenyl or 4-methoxyphenyl.

The precursor intermediates for these three specifically taught compounds have no or almost no herbicidal activity.

DESCRIPTION OF THE INVENTION

Embodiment A of this invention relates to certain novel 2-(2-substituted benzoyl)-cyclohexane-1,3-diones as herbicides. The compounds of this embodiment have the following structural formula ##STR4## wherein R and R¹ are hydrogen, C₁ -C₄ alkyl, preferably methyl or isopropyl, R^(a) OC(O)--, where R^(a) is C₁ -C₄ alkyl; most preferably R and R¹ are hydrogen;

R² is chlorine, bromine, iodine or C₁ -C₄ alkoxy, preferably methoxy; most preferably R₂ is chlorine, bromine or methoxy;

R³, R⁴ and R⁵ independently are hydrogen or an aliphatic group, preferably: (1) hydrogen; (2) halogen, preferably chlorine or bromine; (3) C₁ -C₄ alkyl, preferably methyl; (4) C₁ -C₄ alkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁ -C₄ haloalkyl, more preferably trifluoromethyl; (9) R^(b) SO_(n) -- wherein R^(b) is C₁ -C₄ alkyl, preferably methyl, C₁ -C₄ haloalkyl, phenyl, benzyl, --NR^(d) R^(e) wherein R^(d) and R^(e) independently are hydrogen or C₁ -C₄ alkyl; and n is the integer 0, 1 or 2, preferably 2; ##STR5## wherein R^(c) is C₁ -C₄ alkyl and R^(j) is hydrogen or C₁ -C₄ alkyl, preferably methyl; (11) R^(f) C(O) wherein R^(f) is hydrogen, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy; (12) --NR^(g) R^(h) wherein R^(g) and R^(h) independently are hydrogen or C₁ -C₄ alkyl; or less preferably (13) R³ and R⁴ together can form a ring structure with two adjacent carbon atoms of the phenyl ring.

R³ and R⁴ can also be (14) C₃ -C₅ alkenyloxy (thio) optionally substituted, preferably with halogen or (15) C₃ -C₅ alkynyloxy (thio), optionally substituted, preferably with halogen.

Most preferably, R³ is chlorine, hydrogen, dimethylamino or methoxy. Preferably, R⁴ is hydrogen, chlorine, nitro, SO₂ CH₃, SO₂ N(CH₃)₂ or trifluoromethoxy. Preferably, R⁵ is hydrogen.

Embodiment A' of this invention is an herbicidal composition comprising an herbicidally active 2-benzoyl-1,3-cyclohexanedione and an inert carrier threfor. Preferably, the 2-position of the benzoyl moiety is substituted with chlorine, bromine, iodine or C₁ -C₄ alkoxy; more preferably chlorine, bromine or methoxy; most preferably chlorine. The 5-position of the 1,3-cyclohexanedione moiety can be substituted with one or two C₁ -C₄ alkyl groups, preferably methyl, although such a substitution is not preferred.

The compounds of Embodiment A of this invention can have the following four structural formulae because of tautomerism: ##STR6## wherein R, R¹, R², R³, R⁴ and R⁵ are as defined above.

The circled proton on each of the four tautomers is reasonably labile. These protons are acidic and can be removed by any base to give a salt having an anion of the following four resonance forms: ##STR7## wherein R, R¹, R², R³, R⁴ and R⁵ are as defined above.

Examples of cations of these bases are inorganic cations such as alkali metals, e.g. lithium, sodium, and potassium, alkaline earth metals, e.g. barium, magnesium, calcium and strontium or organic cations such as substituted ammonium, sulfonium or phosphonium wherein the substituent is an aliphatic or aromatic group.

In the above description of the compounds of this invention, alkyl and alkoxy include both straight and branched configurations; for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, and tert-butyl.

Embodiment B of this invention relates to certain novel 2-(2-substituted benzoyl)-cyclohexane-1,3-diones as herbicides. The compounds of this embodiment have the following structural formula ##STR8## wherein R¹⁰ is C₁ -C₆ alkyl, preferably C₁ -C₄, more preferably methyl;

R¹¹ is hydrogen or C₁ -C₆ alkyl, preferably C₁ -C₄, more preferably methyl or ##STR9## wherein R^(a) is C₁ -C₄ alkyl or R¹⁰ and R¹¹ together are alkylene having 3 to 6 carbon atoms, most preferably R¹¹ is hydrogen or methyl;

R¹² is chlorine, bromine, iodine, fluorine or C₁ -C₄ alkoxy, preferably methoxy; most preferably R¹² is chlorine, bromine or methoxy;

R¹³ and R¹⁴ independently are (1) hydrogen or an aliphatic group, preferably hydrogen; (2) halogen, preferably, fluorine, chlorine or bromine; (3) C₁ -C₄ alkyl, preferably methyl; (4) C₁ -C₄ aliphatic alkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁ -C₄ haloalkyl, more preferablyy trifluoromethyl; (9) R^(b) SO_(n) -- wherein R^(b) is C₁ -C₄ alkyl, preferably methyl, C₁ -C₄ haloalkyl, phenyl, benzyl, --NR^(d) R^(e) wherein R^(d) and R^(e) independently are hydrogen or C₁ -C₄ alkyl; and n is the integer 0, 1 or 2, preferably 2; ##STR10## wherein R^(c) is C₁ -C₄ alkyl and R^(j) is hydrogen or C₁ -C₄ alkyl, preferably methyl; (11) R^(f) C(O) wherein R^(f) is hydrogen, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy; (12) --NR^(g) R^(h) wherein R^(g) and R^(h) independently are hydrogen or C₁ -C₄ alkyl; (13) C₁ -C₄ alkylthio or less preferably (14) R¹³ and R¹⁴ together can form a ring structure with two adjacent carbon atoms of the phenyl ring to which they are attached or less preferably (15) R¹³ and R¹⁴ are the groups phenoxy or substituted phenoxy wherein the substituent is halogen or halomethyl or both;

R¹⁵, R¹⁶, R¹⁷ and R¹⁸ are independently the same or different and are selected from the group consisting of hydrogen, C₁ -C₆ alkyl, preferably C₁ -C₄ alkyl, more preferably methyl, most preferably hydrogen or methyl, and their salts;

provided, however, that R¹⁵ and R¹⁶ together may form a substituted or unsubstituted alkylene ring of 2-5 carbon atoms, the preferred substituent being 1 or 2 methyl groups.

More preferably, R¹³ is chlorine, hydrogen, methyl, alkylthio or methoxy. Preferably R¹⁴ is hydrogen, chlorine, nitro, trifluoromethyl, or R^(b) SO_(n) wherein R^(b) is C₁ -C₄ alkyl, preferably methyl and n is the integer 0, 1 or 2, preferably 2.

The compounds of Embodiment B of the invention can have the following four structural formulae because of tautomerism: ##STR11## wherein R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷ and R¹⁸ are as defined above.

The circled proton on each of the four tautomers is reasonably labile. These protons are acidic and can be removed by any base to give a salt having an anion of the following four resonance forms: ##STR12## wherein R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷ and R¹⁸ are as defined above.

Examples of cations of these bases are inorganic cations such as alkali metals e.g. lithium, sodium, and potassium, alkaline earth metals, e.g. barium, magnesium, calcium and strontium, or organic cations such as substituted ammonium, sulfonium or phosphonium wherein the substituent is an aliphatic or aromatic group.

The term "aliphatic group" is used form Embodiments A and B herein in a broad sense to cover a large class of organic groups characterized by being derived from (1) an acylic (open-chain structure) of the paraffin, olefin and acetylene hydrocarbon series and their derivatives or (2) alicyclic compounds. The aliphatic group can have from 1 to 10 carbon atoms.

The term "aromatic group" is used for Embodiments A and B herein in a broad sense to distinguish from the aliphatic group and includes a group derived from (1) compounds having 6 to 20 carbon atoms and characterized by the presence of at least one benzene ring, including monocyclic, bicyclic and polycyclic hydrocarbons and their derivatives and (2) heterocyclic compounds having 5 to 19 carbon atoms which are similar in structure and are characterized by having an unsaturated ring structure containing at least one atom or other than carbon such as nitrogen, sulfur and oxygen and derivatives of these heterocyclic compounds.

In the above description of the compounds of this invention alkyl and alkoxy include both straight and branched configurations; for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, and tert-butyl.

Embodiment C of this invention relates to certain novel 2-(2'-cyanobenzoyl)cyclohexane-1,3-diones as herbicides. The compounds of of this embodiment have the following structural formula ##STR13## wherein R²¹ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferably methyl, most preferably R²¹ is hydrogen or methyl;

R²² is hydrogen; C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferably methyl or ##STR14## wherein R^(a) is C₁ -C₄ alkyl, most preferably R²² is hydrogen or methyl; or R²¹ and R²² together are alkylene having 3 to 6 carbon atoms;

R²³ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferably methyl; most preferably R²³ is hydrogen or methyl;

R²⁴ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferably methyl; most preferably R²⁴ is hydrogen or methyl;

R²⁵ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferably methyl; most preferably R²⁵ is hydrogen or methyl;

R²⁶ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferably methyl, most preferably R²⁶ is hydrogen;

R²⁷ and R²⁸ independently are (1) hydrogen; (2) halogen, preferably chlorine, fluorine or bromine; (39 C₁ -C₄ alkyl, preferably methyl; (4) C₁ -C₄ alkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁ -C₄ haloalkyl, more preferably trifluoromethyl; (9) R^(b) SO_(n) -- wherein n is the integer 0, 1 or 2, preferably 2; and

R^(b) is

(a) C₁ -C₄ alkyl, preferably methyl;

(b) C₁ -C₄ alkyl substituted with halogen or cyano, preferably chloromethyl, trifluoromethyl or cyanomethyl;

(c) phenyl; or

(d) benzyl;

(10) --NR^(c) R^(d) wherein R^(c) and R^(d) independently are hydrogen or C₁ -C₄ alkyl;

(11) R^(e) C(O)-- wherein R^(e) is C₁ -C₄ alkyl or C₁ -C₄ alkoxy; or

(12) --SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are as defined, with the proviso that R²⁷ is not attached to the 6-position.

Preferably, R²⁷ is in the 3-position. Most preferably R²⁷ is hydrogen and R²⁸ is hydrogen, chlorine, bromine, fluorine, trifluoromethyl, or R^(b) SO₂ wherein R^(b) is C₁ -C₄ alkyl, preferably methyl.

Salts of the above-described compounds (as defined hereinafter) are also the subject of the instant invention.

The compounds of this embodiment can have the following four structural formulae because of the tautomerism: ##STR15## wherein R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷ and R²⁸ are as defined above.

The circled proton on each of the four tautomers is reasonably labile. These protons are acidic and can be removed by any base to give a salt having an anion of the following four resonance forms: ##STR16## wherein R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷ and R²⁸ are as defined above.

Examples of cations of these bases are inorgaic cations such as alkali metals e.g. lithium, sodium, and potassium organic cations such as substituted ammonium, sulfonium or phosphonium wherein the substituent is an aliphatic or aromatic group.

Embodiment D of this invention relates to 2-(2-nitrobenzoyl)-1,3-cyclohexanediones and their use as herbicides.

The compounds have a nitro substitution in the 2-position of the phenyl moiety of their compounds. The nitro substitution imparts exceptional herbicidal activity to the compounds of this invention.

Embodiment D' of this invention is an herbicidal composition comprising an herbicidally active 2-(2-nitrobenzoyl)-1,3-cyclohexanedione and an inert carrier therefor. The 4-, 5- and 6-positions of the 1,3-cyclohexanedione moiety can be substituted, preferably with the groups hereinafter recited. More preferably, the 1,3-cyclohexanedione moiety has no substitution or the 4- or 6-positions are substituted with one or two methyl groups. The 3-, 4- and 5-positions of the benzoyl moiety can be substituted, preferably with the groups hereinafter recited.

The novel compounds of Embodiment D have the following structural formula ##STR17## wherein R³¹ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₁₂ alkyl, more preferably methyl, most preferably R³¹ is hydrogen or methyl;

R³² is hydrogen; C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferably methyl or ##STR18## wherein R^(a) is C₁ -C₄ alkyl, most preferably R³² is hydrogen or methyl; or

R³¹ and R³² together are alkylene having 3 to 6 carbon atoms;

R³³ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferably methyl; most preferably R³³ is hydrogen or methyl;

R³⁴ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferably methyl; most preferably R³⁴ is hydrogen or methyl;

R³⁵ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferably methyl; most preferably R³⁵ is hydrogen or methyl;

R³⁶ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferably methyl, most preferably R³⁶ is hydrogen;

R³⁷ and R³⁸ independently are (1) hydrogen; (2) halogen, preferably chlorine, fluorine or bromine; (3) C₁ -C₄ alkyl, preferably methyl; (4) C₁ -C₄ alkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁ -C₄ haloalkyl, most preferably trifluoromethyl; (9) R^(b) SO_(n) -- wherein n is the integer 0, 1 or 2, preferably 2; and

R^(b) is

(a) C₁ -C₄ alkyl, preferably methyl;

(b) C₁ -C₄ alkyl substituted with halogen or cyano, preferably chloromethyl, trifluoromethyl or cyanomethyl;

(c) phenyl; or

(d) benzyl;

(10) --NR^(c) R^(d) wherein R^(c) and R^(d) independently are hydrogen or C₁ -C₄ alkyl; (11) R^(e) C(O)-- wherein R^(e) is C₁ -C₄ alkyl or C₁ -C₄ alkoxy; or (12) --SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are as defined, with the proviso that R³⁷ is not attached to the 6-position.

Preferably, R³⁷ is in the 3-position. Most preferably R³⁷ is hydrogen or C₁ -C₄ alkoxy and R³⁸ is hydrogen, chlorine, bromine, fluorine, trifluoromethyl, or R^(b) SO₂ wherein R^(b) is C₁ -C₄ alkyl, preferably methyl.

The term "C₁ -C₄ alkyl" includes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and t-butyl. The term "halogen" includes chlorine, bromine, iodine and fluorine. The terms "C₁ -C₄ alkoxy" includes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy and t-butoxy. The term "haloalkyl" includes the eight alkyl groups with one or more hydrogens replaced by chlorine, bromine, iodine or fluorine.

Salts of the above-described compounds (as defined hereinafter) are also the subject of the instant invention.

The compounds of this invention can have the following four structural formulae because of tautomerism: ##STR19## wherein R³¹, R³², R³³, R³⁴, R³⁵, R³⁶, R³⁷ and R³⁸ are as defined above.

The circled proton on each of the four tautomers is reasonably labile. These protons are acidic and can be removed by any base to give a salt having an anion of the following four resonance forms: ##STR20## wherein R³¹, R³², R³³, R³⁴, R³⁵, R³⁶, R³⁷ and R³⁸ are as defined above.

Examples of cations of these bases are inorganic cations such as alkali metals e.g. lithium, sodium, and potassium or organic cations such as substituted ammonium, sulfonium or phosphonium wherein the substituent is an aliphatic or aromatic group.

Embodiment E of this invention relates to 2-(2-benzoyl)-1,3-cyclohexanediones and their use as herbicides.

Embodiment E' of this invention is an herbicidal composition comprising an herbicidally active 2-(2-C₁ -C₄ alkylthio, C₁ -C₄ alkylsulfinyl or C₁ -C₄ alkylsulfonyl benzoyl)-1,3-cyclohexanedione and an inert carrier therefor. The 4-, 5- and 6-positions of the 1,3-cyclohexanedione moiety can be substituted, preferably with the groups hereinafter recited. More preferably, the 1,3-cyclohexanedione moiety has no substitution or the 4- or 6-positions are subsituted with one or two methyl groups. The 3-, 4- and 5-positions of the benzoyl moiety can be substituted, preferably with the groups hereinafter recited.

The novel compounds of Embodiment E have the structural formula ##STR21## wherein n is the integer 0, 1 or 2, preferably 2;

R⁴⁰ is C₁ -C₄ alkyl, preferably methyl;

R⁴¹ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferably methyl, most preferably R⁴¹ is hydrogen or methyl;

R⁴² is hydrogen; C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferably methyl or ##STR22## wherein R^(a) is C₁ -C₄, most preferably R⁴² is hydrogen or methyl; or

R⁴¹ and R⁴² together are alkylene having 3 to 6 carbon atoms;

R⁴³ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferably methyl; most preferably R⁴³ is hydrogen or methyl;

R⁴⁴ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferably methyl; most preferably R⁴⁴ is hydrogen or methyl;

R⁴⁵ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferably methyl; most preferably R⁴⁵ is hydrogen or methyl;

R⁴⁶ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferably methyl, most preferably R⁴⁶ is hydrogen;

R⁴⁷ and R⁴⁸ independently are (1) hydrogen; (2) halogen, preferably chlorine, fluorine or bromine; (3) C₁ -C₄ alkyl, preferably methyl; (4) C₁ -C₄ alkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁ -C₄ haloalkyl, more preferably trifluoromethyl; (9) R^(b) SO_(n) -- wherein n is the integer 0, 1 or 2, preferably 2; and

R^(b) is

(a) C₁ -C₄ alkyl, preferably methyl;

(b) C₁ -C₄ alkyl substituted with halogen or cyano, preferably chloromethyl, trifluoromethyl or cyanomethyl;

(c) phenyl; or

(d) benzyl;

(10) --NR^(c) R^(d) wherein R^(c) and R^(d) independently are hydrogen or C₁ -C₄ alkyl; (11) R^(e) C(O)-- wherein R^(e) is C₁ -C₄ alkyl or C₁ -C₄ alkoxy; or (12) --SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are as defined, with the proviso that R⁴⁷ is not attached to the 6-position.

Preferably, R⁴⁷ is in the 3-position. Most preferably R⁴⁷ is hydrogen or 3-chlorine and R⁴⁸ is hydrogen, chlorine, bromine, fluorine, trifluoromethyl, or R^(b) SO₂ wherein R^(b) is C₁ -C₄ alkyl, preferably methyl.

The term "C₁ -C₄ " alkyl includes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and t-butyl. The term "halogen" includes chlorine, bromine, iodine and fluorine. The term "C₁ -C₄ alkoxy" includes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy and t-butoxy. The term "haloalkyl" includes the eight alkyl groups with one or more hydrogens replaced by chloro, bromo, iodo or fluoro.

Salts of the above-described compounds (as defined hereinafter) are also the subject of the instant invention.

The compounds of this invention can have the following four structural formulae because of tautomerism: ##STR23## wherein n, R⁴⁰, R⁴¹, R⁴², R⁴³, R⁴⁴, R⁴⁵, R⁴⁶, R⁴⁷ and R⁴⁸ are as defined above.

The circled proton on each of the four tautomers is reasonably labile. These protons are acidic and can be removed by any base to give a salt having an anion of the following four resonance forms: ##STR24## wherein n, R⁴⁰, R⁴¹, R⁴², R⁴³, R⁴⁴, R⁴⁵, R⁴⁶, R⁴⁷ and R⁴⁸ are as defined above.

Examples of cations of these bases are inorganic cations such as alkali metals e.g. lithium, sodium, and potassium, organic cations such as substituted ammonium, sulfonium or phosphonium wherein the substituent is an aliphatic or aromatic group.

Embodiment F of this invention relates to 2-(2-alkylbenzoyl)-1,3-cyclohexanediones and their use as herbicides.

Embodiment F' of this invention is an herbicidal composition comprising an herbicidally active 2-benzoyl-1,3-cyclohexanedione and an inert carrier therefor wherein the 2-position of the benzoyl moiety is substituted with C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, optionally substituted with halogen, more preferably methyl or trifluoromethyl and the 4-position preferably is substituted with an electron withdrawing group, such as halogen, cyano, trifluoromethyl or nitro. The 4-, 5- and 6-positions of the 1,3-cyclohexanedione moiety can be substituted, preferably with the groups hereinafter recited. More preferably, the 1,3-cyclohexanedione moiety has no substitution or the 4- or 6-positions are substituted with one or two methyl groups. The 3-, 4- and 5-positions of the benzoyl moiety can be substituted, preferably with the groups hereinafter recited.

The novel compounds of Embodiment F have the following structural formula ##STR25## wherein R⁵⁰ is C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, optionally substituted with halogen, more preferably methyl and trifluoromethyl;

R⁵¹ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferably methyl, most preferably R⁵¹ is hydrogen or methyl;

R⁵² is hydrogen; C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferably methyl or ##STR26## wherein R^(a) is C₁ -C₄ alkyl, most preferably R⁵² is hydrogen or methyl; or

R⁵¹ and R⁵² together are alkylene having 3 to 6 carbon atoms;

R⁵³ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferably methyl; most preferably R⁵³ is hydrogen or methyl;

R⁵⁴ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferably methyl; most preferably R⁵⁴ is hydrogen or methyl;

R⁵⁵ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferably methyl; most preferably R⁵⁵ is hydrogen or methyl;

R⁵⁶ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferably methyl, most preferably R⁵⁶ is hydrogen;

R⁵⁷ and R⁵⁸ independently are (1) hydrogen; (2) halogen, preferably chlorine, fluorine or bromine; (3) C₁ -C₄ alkyl, preferably methyl; (4) C₁ -C₄ alkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁ -C₄ haloalkyl, more preferably trifluoromethyl; (9) R^(b) SO_(n) -- wherein n is the integer 0, 1 or 2, preferably 2; and

R^(b) is

(a) C₁ -C₄ alkyl, preferably methyl;

(b) C₁ -C₄ alkyl substituted with halogen or cyano, preferably chloromethyl, trifluoromethyl or cyanomethyl;

(c) phenyl; or

(d) benzyl;

(10) --NR^(c) R^(d) wherein R^(c) and R^(d) independently are hydrogen or C₁ -C₄ alkyl; (11) R^(e) C(O)-- wherein R^(e) is C₁ -C₄ alkyl or C₁ -C₄ alkoxy; or (12) --SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are as defined, with the proviso that R⁵⁷ is not attached to the 6-position.

The term "C₁ -C₄ alkyl" includes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and t-butyl. The term "halogen" includes chlorine, bromine, iodine and fluorine. The term "C₁ -C₄ alkoxy" includes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy and t-butoxy. The term "haloalkyl" includes the eight alkyl groups with one or more hydrogens replaced by chloro, bromo, iodo or fluoro.

Preferably, R⁵⁷ is in the 3-position. Most preferably R⁵⁷ is hydrogen and R⁵⁸ is hydrogen, chlorine, bromine, fluorine, trifluoromethyl, or R^(b) SO₂ wherein R^(b) is C₁ -C₄ alkyl, preferably methyl.

Salts of the above-described compounds (as defined hereinafter) are also the subject of the instant invention.

The compounds of this invention can have the following four structural formulae because of tautomerism: ##STR27## wherein R⁵⁰, R⁵¹, R⁵², R⁵³, R⁵⁴, R⁵⁵, R⁵⁶, R⁵⁷ and R⁵⁸ are as defined above.

The circled proton on each of the four tautomers is reasonably labile. These protons are acidic and can be removed by any base to give a salt having an anion of the following four resonance forms: ##STR28## wherein R⁵⁰, R⁵¹, R⁵², R⁵³, R⁵⁴, R⁵⁵, R⁵⁶, R⁵⁷ and R⁵⁸ are as defined above.

Examples of cations of these bases are inorganic cations such as alkali metals e.g. lithium, sodium, and potassium organic cations such as substituted ammonium, sulfonium or phosphonium wherein the substituent is an aliphatic or aromatic group.

Embodiment G of this invention relates to 2-benzoyl-1,3,5-cyclohexanetriones and their use as herbicides.

Embodiment G' of this invention is an herbicidal composition comprising an herbicidally active 2-benzoyl-substituted-1,3,5-cyclohexanetrione and an inert carrier therefor. The 4- and 6-positions of the 1,3,5-cyclohexanetrione moiety are preferably substituted with groups hereinafter defined, most preferably with all methyl groups. The benzoyl moiety can be substituted, preferably with the groups hereinafter recited.

The novel compounds of Embodiment G have the following structural formula ##STR29## wherein R⁶⁰ is hydrogen; halogen; C₁ -C₂ alkyl, preferably methyl; C₁ -C₂ alkoxy, preferably methoxy; nitro; cyano; C₁ -C₂ haloalkyl, preferably trifluoromethyl; R^(a) SO_(n) -- wherein n is 0 or 2, preferably 2 and R^(a) is C₁ -C₂ alkyl, preferably methyl, trifluoromethyl or difluoromethyl; or trifluoromethoxy or difluoromethoxy. Preferably, R⁶⁰ is chlorine, bromine, C₁ -C₂ alkyl, C₁ -C₂ alkoxy, trifluoromethyl, cyano, nitro, C₁ -C₂ alkylthio or C₁ -C₂ alkylsulfonyl; more preferably chlorine, nitro, methyl, trifluoromethyl or methylsulfonyl; and

R⁶¹ is hydrogen or C₁ -C₄ alkyl, preferably methyl;

R⁶² is hydrogen or C₁ -C₄ alkyl, preferably methyl; or

R⁶¹ and R⁶² together are C₂ -C₅ alkylene;

R⁶³ is C₁ -C₄ alkyl, preferably methyl;

R⁶⁴ is C₁ -C₄ alkyl, preferably methyl; or

R⁶³ and R⁶⁴ together are C₂ -C₅ alkylene;

R⁶⁵ and R⁶⁶ independently are (1) hydrogen; (2) halogen, preferably chlorine, fluorine or bromine; (3) C₁ -C₄ alkyl, preferably methyl; (4) C₁ -C₄ alkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁ -C₄ haloalkyl, more preferably trifluoromethyl; (9) R^(b) SO_(n) -- wherein n is the integer 0, 1 or 2, preferably 2; and

R^(b) is

(a) C₁ -C₄ alkyl, preferably methyl;

(b) C₁ -C₄ alkyl substituted with halogen or cyano, preferably chloromethyl, trifluoromethyl or cyanomethyl;

(c) phenyl; or

(d) benzyl;

(10) --NR^(c) R^(d) wherein R^(c) and R^(d) independently are hydrogen or C₁ -C₄ alkyl; (11) R^(e) C(O)-- wherein R^(e) is C₁ -C₄ alkyl or C₁ -C₄ alkoxy; (12) --SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are as defined; or (13) --N(R^(c))C(O)R^(d) wherein R^(c) and R^(d) are as defined.

Preferably R⁶⁵ is in the 3-position. More preferably R⁶⁵ is hydrogen, chlorine, fluorine, trifluoromethyl, cyano, C₁ -C₄ alkoxy or C₁ -C₄ thioalkyl. Most preferably, R⁶⁵ is hydrogen. Preferably R⁶⁶ is in the 4-position. Most preferably R⁶⁶ is halogen, cyano, trifluoromethyl, or R^(b) SO₂ wherein R^(b) is C₁ -C₄ alkyl, preferably methyl or C₁ -C₄ haloalkyl, preferably chloromethyl, difluoromethyl or trifluoromethyl.

The term "C₁ -C₄ alkyl" includes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and t-butyl. The term "halogen" includes chlorine, bromine, iodine and fluorine. The terms "C₁ -C₄ alkoxy" includes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy and t-butoxy. The term "C₁ -C₄ haloalkyl" includes the alkyl groups defined above under C₁ -C₄ alkyl in which one or more hydrogens is replaced by chlorine, bromine, iodine or fluorine.

Salts of the above-described compounds (as defined hereinafter) are included within the scope of the instant invention.

The compounds of this invention can have the following four structural formulae because of tautomerism: ##STR30## wherein R⁶⁰, R⁶¹, R⁶², R⁶³, R⁶⁴, R⁶⁵ and R⁶⁶ are as defined above.

The circled proton on each of the four tautomers is reasonably labile. These protons are acidic and can be removed by reaction with a base to form a salt having an anion of the following four resonance forms: ##STR31## wherein R⁶⁰, R⁶¹, R⁶², R⁶³, R⁶⁴, R⁶⁵ and R⁶⁶ are as defined above.

Examples of cations of these bases are inorganic cations such as alkalimetals, e.g., lithium, sodium and potassium; the alkaline earth metals, e.g. calcium and magnesium or ammonium or organic cations such as substituted ammonium, sulfonium, sulfoxonium or phosphonium wherein the substituents are aliphatic or aromatic groups.

Those skilled in the art will recognize in considering the salts of this invention that varying degrees os association between the anion and cation will exist depending upon the nature of the cation. In some instances with a suitable cation, such as copper, the salt can exist in a chelated form.

The compounds of this invention and their salts are active herbicides of a general type. That is, they are herbicidally effective against a wide range of plant species. The method of controlling undesirable vegetation of the present invention comprises applying an herbicidally effective amount of the above-described compounds to the area where control is desired.

The compounds of Embodiments A and A' of the present invention can be prepared by the following general method. ##STR32##

Generally, mole amounts of the dione and substituted benzoyl cyanide are used, along with a slight mole excess of zinc chloride. The two reactants and the zinc chloride are combined in a solvent such as methylene chloride. A slight mole excess of triethylamine is slowly added to the reaction mixture with cooling. The mixture is stirred at room temperature for 5 hours.

The reaction product is worked up by conventional techniques.

The above-described substituted benzoyl cyanide can be prepared according to the teaching of T. S. Oakwood and C. A. Weisgerber, Organic Synthesis Collected, Vol. III, pp. 122 (1955).

The following example teaches the synthesis of a representative compound of Embodiments A and A' of this invention.

EXAMPLE 1-A,A' 2-(2,4-Dichlorobenzoyl)-cyclohexane-1,3-dione ##STR33##

1,3-Cyclohexanedione [11.2 grams (g), 0.1 mole], 20.0 g (0.1 mole) 2,4-dichlorobenzoyl cyanide and 13.6 g (0.11 mole) anhydrous, powdered zinc chloride were combined in 100 milliliters (ml) methylene chloride. Triethylamine (10.1 g, 0.12 mole) was slowly added with cooling. The reaction mixture was stirred at room temperature for 5 hours and then poured into 2N hydrochloric acid. The aqueous phase was discarded and the organic phase was washed with 150 ml 5% Na₂ CO₃ four times. The aqueous washings were combined and acidified with HCl, extracted with methylene chloride, dried and concentrated to yield 25.3 g of crude product. The crude product was dissolved in ether and stirred with 250 ml of 5% copper (II) acetate. The resulting copper salt was filtered, washed with ether and stirred with 6N hydrochloric acid to destroy the salt. The extract was washed with ether to yield 22.15 grams of the desired product m.p. 138°-140° C. (77.7% yield). The structure was confirmed by instrumental analysis.

The compounds of Embodiment B of the present invention can be prepared by the following general method. ##STR34##

Generally, mole amounts of the dione and substituted benzoyl cyanide are used, along with a slight mole excess of zinc chloride. The two reactants and the zinc chloride are combined in a solvent such as methylene chloride. A slight mole excess of triethylamine is slowly added to the reaction mixture with cooling. The mixture is stirred at room temperature for 5 hours.

The reaction product is worked up by conventional techniques.

The above-described substituted benzoyl cyanide can be prepared according to the teaching of T. S. Oakwood and C. A. Weisgerber, Organic Synthesis Collected, Vol. III, pp. 122 (1955).

The following example teaches the synthesis of a representative compound of Embodiment B of this invention.

EXAMPLE 1-B 4,4-Dimethyl-2-(2,4-dichlorobenzoyl)-cyclohexane-1,3-dione ##STR35##

4,4-Dimethyl-1,3-cyclohexanedione [14.0 grams (g), 0.1 mole], 20.0 g (0.1 mole) 2,4-dichlorobenzoyl cyanide and 13.6 g (0.11 mole) anhydrous, powdered zinc chloride were combined in 100 milliliters (ml) methylene chloride. Triethylamine (10.1 g, 0.12 mole) was slowly added with cooling. The reaction mixture was stirred at room temperature for 5 hours and then poured into 2N hydrochloric acid. The aqueous phase was discarded and the organic phase was washed with 150 ml 5% Na₂ CO₃ four times. The aqueous washings were combined and acidified with HCl, extracted with methylene chloride, dried and concentrated to yield 25.3 g of crude product. The crude product was chromatographed (2% AcOH/CH₂ Cl₂) in 5 g aliquots then reduced on rotavap under reduced pressure at 50° C. for 30 minutes to remove AcOH. This yielded an oil (40% yield). The structure was confirmed by instrumental analysis.

The compounds of Embodiment C of the present invention can be prepared by the following general method. ##STR36##

Generally, in step (1) mole amounts of the dione and substituted benzoyl chloride are used, along with a slight mole excess of triethylamine. The two reactants are combined in a solvent such as methylene chloride. The triethylamine is slowly added to the reaction mixture with cooling. The mixture is stirred at room temperature for several hours.

The reaction product is worked up by conventional techniques. ##STR37##

Generally, in step (2) a mole of the enol ester intermediate is reacted with 1 to 4 moles of the triethylamine, preferably 2 moles of the triethylamine and up to 0.5 mole, preferably 0.1 mole of a cyanide source (e.g., potassium cyanide or acetone cyanohydrin). The mixture is stirred in a reaction pot for about one hour at room temperature and the desired product is recovered by conventional techniques.

The above described substituted benzoyl chlorides can be prepared from the corresponding substituted benzoic acids according to the teaching of Reagents for Organic Synthesis, Vol. I, L. F. Fieser and M. Fieser, pp. 767-769 (1967). ##STR38## wherein R²⁷ and R²⁸ are as previously defined.

The substituted benzoic acids can be prepared by a wide variety of general methods according to the teaching of The Chemistry of Carboxylic Acids and Esters, S. Patai, editor, J. Wiley and Sons, New York, N.Y. (1969) and Survey of Organic Synthesis, C. A. Buehler and D. F. Pearson, J. Wiley and Sons, (1970).

The following are two representative examples of the methods described therein. ##STR39## wherein R²⁷ and R²⁸ are as previously defined.

In reaction (a) the substituted acetophenone is heated to reflux for several hours in an aqueous hypochlorite solution. The mixture is cooled and the reaction product is isolated by conventional techniques. ##STR40## wherein R²⁷ and R²⁸ are as previously defined.

In reaction (b) the substituted toluene is heated to reflux in an aqueous solution of potassium permanganate for several hours. The solution is then filtered and the reaction product is isolated by conventional techniques.

The following example teaches the synthesis of a representative compound of Embodiment C of this invention.

EXAMPLE 1-C 2-(2'-Cyanobenzoyl)-4,4-dimethyl-1,3-cyclohexanedione ##STR41##

2-Cyanobenzoyl chloride (3.9 g, 24 mmol) and 4,4-dimethyl-1,3-cyclohexanedione (3.3 g, 24 mmol) were dissolved in 75 ml methylene chloride. Triethylamine (5.0 ml, 36 mmol) was added dropwise and the resulting solution stirred for one and one-half hours at room temperature. The solution was washed with water, 2 normal hydrochloric acid (2N HCl), 5% potassium carbonate solution (5% K₂ CO₃) and saturated sodium chloride solution (brine), dried over anhydrous magnesium sulfate (MgSO₄) and concentrated under vacuum. The residue was dissolved in 20 ml acetonitrile. Triethylamine (4.4 ml, 32 mmol) and acetone cyanohydrin (5 drops) were added and the solution stirred for two hours. After dilution with ether, the solution was washed with 2N HCl and extracted with 5% K₂ CO₃. The aqueous extract was acidified with concentrated hydrochloric acid and extracted with ether. The ether was washed with water and brine, dried (MgSO₄) and concentrated under vacuum. The residue was purified by silica gel chromatography, yielding 1.2 g of a viscous oil which was identified as the desired compound by nuclear magnetic resonance spectroscopy, infrared spectroscopy and mass spectroscopy.

The compounds of Embodiments D and D' of the present invention can be prepared by the following two-step general method.

The process proceeds via the production of an enol ester intermediate as shown in reaction (1). The final product is obtained by rearrangement of the enol ester as shown in reaction (2). The two reactions may be conducted as separate steps by isolation and recovery of the enol ester using conventional techniques prior to conducting step (2), or by addition of a cyanide source to the reaction medium after the formation of the enol ester, or in one step by inclusion of the cyanide source at the start of reaction (1). ##STR42## wherein R³¹ through R³⁸ and moderate base are as defined and X is halogen, preferably chlorine, C₁ -C₄ alkyl-C(O)--O--, C₁ -C₄ alkoxy-C(O)--O-- or ##STR43## wherein R³⁷ and R³⁸ in this portion of the molecule are identical with those in the reactant shown above and the moderate base is as defined, preferably tri-C₁ -C₆ alkylamine, alkali metal carbonate or alkali metal phosphate.

Generally, in step (1) mole amounts of the dione and substituted benzoyl reactant are used, along with a mole amount or excess of the base. The two reactants are combined in an organic solvent such as methylene chloride, toluene, ethyl acetate or dimethylformamide. The base or benzoyl reactant preferably are added to the reaction mixture with cooling. The mixture is stirred at 0° C.-50° C. until the reaction is substantially complete. ##STR44## wherein the moderate base and R³¹ through R³⁸ are as defined above.

Generally, in step (2) a mole of the enol ester intermediate is reacted with 1 to 4 moles of the base, preferably about 2 moles of moderate base and from 0.01 mole to about 0.5 mole or higher, preferably around 0.1 mole of the cyanide source (e.g., potassium cyanide or acetone cyanohydrin). The mixture is stirred in a reaction pot until the rearrangement is substantially complete at a temperature below 50° C., preferably about 20° C. to about 40° C., and the desired product is recovered by conventional techniques.

The term "cyanide source" refers to a substance or substances which under the rearrangement conditions consists of or generates hydrogen cyanide and/or cyanide anion.

The process is conducted in the presence of a catalytic amount of a source of cyanide anion and/or hydrogen cyanide, together with a molar excess, with respect to the enol ester, of a moderate base.

Preferred cyanide sources are alkali metal cyanides such as sodium and potassium cyanide; cyanohydrins of methyl alkyl ketones having from 1-4 carbon atoms in the alkyl groups, such as acetone or methyl isobutyl ketone cyanohydrins; cyanohydrins of benzaldehyde or of C₂ -C₅ aliphatic aldehydes such as acetaldehyde, propionaldehyde, etc., cyanohydrins; zinc cyanide; tri(lower alkyl) silyl cyanides, notably trimethyl silyl cyanide; and hydrogen cyanide itself. Hydrogen cyanide is considered most advantageous as it produces relatively rapid reaction and is inexpensive. Among cyanohydrins the preferred cyanide source is acetone cyanohydrin.

The cyanide source is used in an amount up to about 50 mole percent based on the enol ester. It may be used in as little as about 1 mole percent to produce an acceptable rate of reaction at about 40° C. on a small scale. Larger scale reactions give more reproducible results with slightly higher catalyst levels of about 2 mole percent. Generally about 1-10 mole % of the cyanide source is preferred.

The process is conducted with a molar excess, with respect to the enol ester, of a moderate base. By the term "moderate base" is meant a substance which acts as a base yet whose strength or activity as a base lies between that of strong bases such as hydroxides (which could cause hydrolysis of the enol ester) and that of weak bases such as bicarbonates (which would not function effectively). Moderate bases suitable for use in this embodiment include both organic bases such as tertiary amines and inorganic bases such as alkali metal carbonates and phosphates. Suitable tertiary amines include trialkylamines such as triethylamine. Suitable inorganic bases include potassium carbonate and trisodium phosphate.

The base is used in an amount of from about 1 to about 4 moles per mole of enol ester, preferably about 2 moles per mole.

When the cyanide source is an alkali metal cyanide, particularly potassium cyanide, a phase transfer catalyst may be included in the reaction. Particularly suitable phase transfer catalysts are the Crown ethers.

A number of different solvents may be usable in this process, depending on the nature of the acid chloride or the acylated product. A preferred solvent for this reaction is 1,2-dichloroethane. Other solvents which may be employed, depending on the reactants or products include toluene, acetonitrile, methylene chloride, ethyl acetate, dimethylformamide, and methyl isobutyl ketone (MIBK).

In general, depending on the nature of the reactants and the cyanide source, the rearrangementt may be conducted at temperatures up to about 50° C.

The above described substituted benzoyl chlorides can be prepared from the corresponding substituted benzoic acids according to the teaching of Reagents for Organic Synthesis, Vol. I, L. F. Fieser and M. Fieser, pp. 767-769 (1967). ##STR45## wherein R³⁷ and R³⁸ are as previously defined.

The substituted benzoic acids can be prepared by a wide variety of general methods according to the teaching of The Chemistry of Carboxylic Acids and Esters, S. Patai, editor, J. Wiley and Sons, New York, N.Y. (1969) and Survey of Organic Synthesis, C. A. Buehler and D. F. Pearson, J. Wiley and Sons, (1970).

The following are three representative examples of the methods described therein. ##STR46## wherein R³⁷ and R³⁸ are as previously defined.

In reaction (a) the substituted benzonitrile is heated to reflux in aqueous sulfuric acid for several hours. The mixture is cooled and the reaction product is isolated by conventional techniques. ##STR47## wherein R³⁷ and R³⁸ are as previously defined.

In reaction (b) the substituted acetophenone is heated to reflux for several hours in an aqueous hypochlorite solution. The mixture is cooled and the reaction product is isolated by conventional techniques. ##STR48## wherein R³⁷ and R³⁸ are as previously defined.

In reaction (c) the substituted toluene is heated to reflux in an aqueous solution of potassium permanganate for several hours. The solution is then filtered and the reaction product is isolated by conventional techniques.

The following examples teach the synthesis of representative compounds of Embodiment D and D' of this invention.

EXAMPLE 1-D,D' 2-(2'-Nitrobenzoyl)-1,3-cyclohexanedione ##STR49##

2-Nitrobenzoyl chloride (5.0 g, 27 mmol) and cyclohexanedione (3.0 g, 27 mmol) were dissolved in methylene chloride. Triethylamine (4.9 ml, 35 mmol) was added dropwise and the resulting solution stirred for one hour. The solution was washed with 2 normal hydrochloric acid (2N HCl), water, 5% potassium carbonate solution and saturated sodium chloride solution, dried over anhydrous magnesium sulfate (MgSO₄) and concentrated under vacuum. The residue was dissolved in 20 ml acetonitrile. Triethylamine (1 equivalent) and potassium cyanide (40 mol%) were added and the solution stirred for one hour at room temperature. After dilution with ether, the solution was washed with 2N HCl and extracted with 5% potassium carbonate solution. The aqueous extract was acidified and ether was added. Filtration of the resulting mixture yielded 3.2 g of the desired compound (m.p. 132°-135° C.) which was identified by nuclear magnetic resonance spectroscopy, infrared spectroscopy and mass spectroscopy.

EXAMPLE 2-D,D' 2-(2'-Nitrobenzoyl)-5,5-dimethyl-1,3-cyclohexanedione ##STR50##

Triethylamine (3.4 ml, 25 mmol) was added dropwise to a methylene chloride solution of 2-nitrobenzoyl chloride (3.5 g, 19 mmol) and 5,5-dimethylcyclohexanedione (2.4 g, 19 mmol). After stirring for one hour at room temperature an additional 3 equivalents of triethylamine and 0.4 ml acetone cyanohydrin were added. The solution was stirred for 2.5 hours, then washed with 2N HCl and extracted with 5% potassium carbonate solution. The basic extracts were acidified with 2N HCl and extracted with ether. The ether portion was washed with saturated sodium chloride solution, dried over anhydrous magnesium sulfate and concentrated under vacuum. The residue was recrystallized from ethyl acetate yielding 2.0 g of the desired compound (m.p. 130°-133° C.) which was identified as such by nuclear magnetic resonance spectroscopy, infrared spectroscopy and mass spectroscopy.

The compounds of Embodiments E and E' of the present invention can be prepared by the following two or three step general method.

The process proceeds via the production of an enol ester intermediate as shown in reaction (1). The final product is obtained by rearrangement of the enol ester as shown in reaction (2). The two reactions may be conducted as separate steps by isolation and recovery of the enol ester using conventional techniques prior to conducting step (2), or by addition of a cyanide source to the reaction medium after the formation of the enol ester, or in one step by inclusion of the cyanide source at the start of reaction (1). ##STR51## wherein moderate base, and R⁴⁰ through R⁴⁸ are defined herein, and X is halogen, preferably chlorine, C₁ -C₄ alkyl-C(O)--O--, C₁ -C₄ alkoxy-C(O)--O-- or ##STR52## wherein R⁴⁰, R⁴⁷ and R⁴⁸ in this portion of the moledule are identical with those in the reactant shown above, and the moderate base is as defined, preferably tri-C₁ -C₆ alkylamine, alkali metal carbonate or alkali metal phosphate.

Generally, in step (1) mole amounts of the dione and substituted benzoyl reactant are used, along with a mole amount or excess of the base. The two reactants are combined in an organic solvent such as methylene chloride, toluene, ethyl acetate or dimethylformamide. The base or benzoyl reactant preferably are added to the reaction mixture with cooling. The mixture is stirred at 0° C.-50° C. until the reaction is substantially complete. ##STR53##

Generally, in step (2) a mole of the enol ester intermediate is reacted with 1 to 4 moles of the base, preferably about 2 moles of moderate base and from 0.01 mole to about 0.5 mole or higher, preferably around 0.1 mole of the cyanide source (e.g., potassium cyanide or acetonecyanohydrin). The mixture is stirred in a reaction pot until the rearrangement is substantially complete at a temperature below 50° C., preferably about 20° C. to about 40° C., and the desired product is recovered by conventional techniques.

The terms "cyanide source" refers to a substance or substances which under the rearrangement conditions consists of or generates hydrogen cyanide and/or cyanide anion.

The process is conducted in the presence of a catalytic amount of a source of cyanide anion and/or hydrogen cyanide, together with a molar excess, with respect to the enol ester, of a moderate base.

Preferred cyanide sources are alkali metal cyanides such as sodium and potassium cyanide; cyanohydrins of methyl alkyl ketones having from 1-4 carbon atoms in the alkyl groups, such as acetone or methyl isobutyl ketone cyanohydrins; cyanohydrins of benzaldehyde or of C₂ -C₅ aliphatic aldehydes such as acetaldehyde, propionaldehyde, etc., cyanohydrins; zinc cyanide; tri(lower alkyl) silyl cyanides, notably trimethyl silyl cyanide; and hydrogen cyanide itself. Hydrogen cyanide is considered most advantageous as it produces relatively rapid reaction and is inexpensive. Among cyanohydrins the preferred cyanide source is acetone cyanohydrin.

The cyanide source is used in an amount up to about 50 mole percent based on the enol ester. It may be used in as little as about 1 mole percent to produce an acceptable rate of reaction at about 40° C. on a small scale. Larger scale reactions give more reproducible results with slightly higher catalyst levels of about 2 mole percent. Generally about 1-10 mole % of the cyanide source is preferred.

The process is conducted with a molar excess, with respect to the enol ester, of a moderate base. By the term "moderate base" is meant a substance which acts as a base yet whose strength or activity as a base lies between that of strong bases such as hydroxides (which could cause hydrolysis of the enol ester) and that of weak bases such as bicarbonates (which would not function effectively). Moderate bases suitable for use in this embodiment include both organic bases such as tertiary amines and inorganic bases such as alkali metal carbonates and phosphates. Suitable tertiary amines include trialkylamines such as triethylamine. Suitable inorganic bases include potassium carbonate and trisodium phosphate.

The base is used in an amount of from about 1 to about 4 moles per mole of enol ester, preferably about 2 moles per mole.

When the cyanide source is an alkali metal cyanide, particularly potassium cyanide, a phase transfer catalyst may be included in the reaction. Particularly suitable phase transfer catalysts are the Crown ethers.

A number of different solvents may be usable in this process, depending on the nature of the acid chloride or the acylated product. A preferred solvent for this reaction is 1,2-dichloroethane. Other solvents which may be employed, depending on the reactants or products include toluene, acetonitrile, methylene chloride, ethyl acetate, dimethylformamide, and methyl isobutyl ketone (MIBK).

In general, depending on the nature of the reactants and the cyanide source, the rearrangement may be conducted at temperatures up to about 50° C. ##STR54## wherein n is 1 or 2.

Generally in step (3), a mole of the reaction product of step (2) is reacted with a slight mole or two mole excess of of an oxidizing agent such as m-chloroperbenzoic acid after being dissolved in a solvent such as methylene chloride. After completion of the reaction, the resulting mixture is stripped under vacuum. The residue is purified by silica gel chromatography to yield the desired product.

The above described substituted benzoyl chlorides can be prepared from the corresponding substituted benzoic acids according to the teaching of Reagents for Organic Synthesis, Vol. I, L. F. Fieser and M. Fieser, pp. 767-769 (1967). ##STR55## wherein R⁴⁰, R⁴⁷ and R⁴⁸ are as previously defined.

The substituted benzoic acids can be prepared by a wide variety of general methods according to the teaching of The Chemistry of Carboxylic Acids and Esters, S. Patai, editor, J. Wiley and Sons, New York, N.Y. (1969) and Survey of Organic Synthesis, C. A. Buehler and D. F. Pearson, J. Wiley and Sons, (1970).

The following are three representative examples of the methods described therein. ##STR56## wherein R⁴⁰, R⁴⁷ and R⁴⁸ are as previously defined.

In reaction (a) the substituted benzonitrile is heated to reflux in aqueous sulfuric acid for several hours. The mixture is cooled and the reaction product is isolated by conventional techniques. ##STR57## wherein R⁴⁰, R⁴⁷ and R⁴⁸ are as previously defined.

In reaction (b) the substituted acetophenone is heated to reflux for several hours in an aqueous hypochlorite solution. The mixture is cooled and the reaction product is isolated by conventional techniques. ##STR58## wherein R⁴⁰, R⁴⁷ and R⁴⁸ are as defined and X is chlorine, bromine or iodine.

In reaction (c) the substituted aromatic halide is allowed to react with magnesium in a solvent such as ether. The solution is then poured over crushed dry ice and the benzoic acid is isolated by conventional techniques.

The following examples teach the synthesis representative compounds of Embodiments E and E' of this invention.

EXAMPLE 1-E,E' 2-(2'-Methylthiobenzoyl)-4,4,6-trimethyl-1,3-cyclohexanedione ##STR59##

2-Methylthiobenzoyl chloride (7.2 g, 39 mmol) and 4,4,6-trimethylcyclohexanedione (5.0 g, 39 mmol) were dissolved in methylene chloride. Triethylamine (7.0 ml, 50 mmol) was added dropwise and the resulting solution stirred for one hour at room temperature. The solution was washed with 2 normal hydrochloric acid (2N HCl), 5% potassium carbonate solution (5% K₂ CO₃) and saturated sodium chloride solution (brine), dried over anhydrous magnesium sulfate (MgSO₄) and concentrated under vacuum. The residue was dissolved in 20 ml acetonitrile. Triethylamine (2.5 equivalents) and acetone cyanohydrin (0.4 ml) were added and the solution stirred for 45 minutes at room temperature. After dilution with ether, the solution was washed with 2N HCl and extracted with 5% K₂ CO₃. The aqueous extract was acidified with hydrochloric acid and extracted with ether. The ether was washed with brine, dried (MgSO₄) and concentrated under vacuum. The residue was purified by trituration with ether, yielding 5.0 g of a viscous oil which was identified as the desired compound by nuclear magnetic resonance spectroscopy (nmr), infrared spectroscopy (ir) and mass spectroscopy (ms).

EXAMPLE 2-E,E' 2-(2'-Methanesulfonylbenzoyl)-4,4,6-trimethyl-1,3-cyclohexanedione ##STR60##

The benzoyl cyclohexanedione prepared in Example 1 (2.5 g, 7.9 mmol) was dissolved in 40 ml methylene chloride. m-Chloroperbenzoic acid (3.5 g, 16 mmol) was added and the resulting solution was stirred for 45 minutes. The solution was concentrated under vacuum. Purification of the residue by silica gel chromatography yielded 1.7 g of a viscous oil which was identified as the desired compound by nmr, ir and ms.

EXAMPLE 3-E,E' 2-(4'-Trifluoromethyl-2'-methanesulfinylbenzoyl)-4,4-dimethyl-1,3-cyclohexanedione ##STR61##

2-(4'-Trifluoromethyl-2'-methylthiobenzoyl)-4,4-dimethyl-1,3-cyclohexanedione (5.0 g, 14 mmol) (which was prepared according to the method of Example 1) was dissolved in 50 ml methylene chloride. A solution of m-chloroperbenzoic acid (2.4 g.-80%, 14 mmol) in 50 ml methylene chloride was added dropwise and the resulting solution was stirred for three hours at room temperature. After concentration under vacuum, the residue was dissolved in ether and washed with 1% hydrochloric acid. A 5% copper(II) acetate solution was added to the ether fraction, followed by hexane. The liquid phase was decanted and the remaining gummy solid stirred with 6N HCl and ether. The ether layer was dried (MgSO₄) and concentrated to give 4.7 of a thick yellow solid. Purification on a centrifugally accelerated thin layer chromatograph (4 mm silica gel, 50:50:1 hexane:ethyl acetate:acetic acid-eluent) yielded 2.4 g of a viscous oil which was identified as the desired compound by nmr, ir and ms.

The compounds of Embodiments F and F' of the present invention can be prepared by the following two-step general method.

The process proceeds via the production of an enol ester intermediate as shown in reaction (1). The final product is obtained by rearrangement of the enol ester as shown in reaction (2). The two reactions may be conducted as separate steps by isolation and recovery of the enol ester using conventional techniques prior to conducting step (2), or by addition of a cyanide source to the reaction medium after the formation of the enol ester, or in one step by inclusion of the cyanide source at the start of reaction (1). ##STR62## wherein R⁵⁰ through R⁵⁸ are as defined and X is halogen, preferably chlorine, C₁ -C₄ alkyl-C(O)--O--, C₁ -C₄ alkoxy-C(O)--O-- or ##STR63## wherei R⁵⁰, R⁵⁷ and R⁵⁸ in this portion of the molecule are identical with those in the reactant shown above and the moderate base is as defined, preferably tri-C₁ -C₆ alkylamine, alkali metal carbonate or alkali metal phosphate.

Generally, in step (1) mole amounts of the dione and substituted benzoyl reactant are used, along with a mole amount or excess of the base. The two reactants are combined in an organic solvent such as methylene chloride, toluene, ethyl acetate or dimethylformamide. The base or benzoyl reactant preferably are added to the reaction mixture with cooling. The mixture is stirred at 0° C.-50° C. until the reaction is substantially complete.

The reaction product is worked up by conventional techniques. ##STR64## wherein R⁵⁰ through R⁵⁸ are as defined.

Generally, in step (2) a mole of the enol ester intermediate is reacted with 1 to 4 moles of the base, preferably about 2 moles of moderate base and from 0.01 mole to about 0.5 mole or higher, preferably around 0.1 mole of the cyanide source (e.g., potassium cyanide or acetone cyanohydrin). The mixture is stirred in a reaction pot until the rearrangement is substantially complete at a temperature below 80° C., preferably about 20° C. to about 40° C., and the desired product is recovered by conventional techniques.

The term "cyanide source" refers to a substance or substances which under the rearrangement conditions consists of or generates hydrogen cyanide and/or cyanide anion.

The process is conducted in the presence of a catalytic amount of a source of cyanide anion and/or hydrogen cyanide, together with a molar excess, with respect to the enol ester, of a moderate base.

Preferred cyanide sources are alkali metal cyanides such as sodium and potassium cyanide; cyanohydrins of methyl alkyl ketones having from 1-4 carbon atoms in the alkyl groups, such as acetone or methyl isobutyl ketone cyanohydrins; cyanohydrins of benzaldehyde or of C₂ -C₅ aliphatic aldehydes such as acetaldehyde, propionaldehyde, etc., cyanohydrins; zinc cyanide; tri(lower alkyl) silyl cyanides, notably trimethyl silyl cyanide; and hydrogen cyanide itself. Hydrogen cyanide is considered most advantageous as it produces relatively rapid reaction and is inexpensive. Among cyanohydrins the preferred cyanide source is acetone cyanohydrin.

The cyanide source is used in an amount up to about 50 mole percent based on the enol ester. It may be used in as little as about 1 mole percent to produce an acceptable rate of reaction at about 40° C. on a small scale. Larger scale reactions give more reproducible results with slightly higher catalyst levels of about 2 mole percent. Generally about 1-10 mole % of the cyanide source is preferred.

The process is conducted with a molar excess, with respect to the enol ester, of a moderate base. By the term "moderate base" is meant a substance which acts as a base yet whose strength or activity as a base lies between that of strong bases such as hydroxides (which could cause hydrolysis of the enol ester) and that of weak bases such as bicarbonates (which would not function effectively). Moderate bases suitable for use in this embodiment include both organic bases such as tertiary amines and inorganic bases such as alkali metal carbonates and phosphates. Suitable tertiary amines include trialkylamines such as triethylamine. Suitable inorganic bases include potassium carbonate and trisodium phosphate.

The base is used in an amount of from about 1 to about 4 moles per mole of enol ester, preferably about 2 moles per mole.

When the cyanide source is an alkali metal cyanide, particularly potassium cyanide, a phase transfer catalyst may be included in the reaction. Particularly suitable phase transfer catalysts are the Crown ethers.

A number of different solvents may be usable in this process, depending on the nature of the acid chloride or the acylated product. A preferred solvent for this reaction is 1,2-dichloroethane. Other solvents which may be employed, depending on the reactants or products include toluene, acetonitrile, methylene chloride, ethyl acetate, dimethylformamide, and methyl isobutyl ketone (MIBK).

In general, depending on the nature of the reactants and the cyanide source, the rearrangement may be conducted at temperatures up to about 50° C.

The above described substituted benzoyl chlorides can be prepared from the corresponding substituted benzoic acids according to the teaching of Reagents for Organic Synthesis, Vol. I, L. F. Fieser and M. Fieser, pp. 767-769 (1967). ##STR65## wherein R⁵⁰, R⁵⁷ and R⁵⁸ are as previously defined.

The substituted benzoic acids can be prepared by a wide variety of general methods according to the teaching of The Chemistry of Carboxylic Acids and Esters, S. Patai, editor, J. Wiley and Sons, New York, N.Y. (1969) and Survey of Organic Synthesis, C. A. Buehler and D. F. Pearson, J. Wiley and Sons, (1970).

The following are four representative examples of the methods described therein. ##STR66## wherein R⁵⁰, R⁵⁷ and R⁵⁸ are as previously defined.

In reaction (a) the substituted benzonitrile is heated to reflux in aqueous sulfuric acid for several hours. The mixture is cooled and the reaction product is isolated by conventional techniques. ##STR67## wherein R⁵⁰, R⁵⁷ and R⁵⁸ are as previously defined.

In reaction (b) the substituted acetophenone is heated to reflux for several hours in an aqueous hypochlorite solution. The mixture is cooled and the reaction product is isolated by conventional techniques. ##STR68## wherein R⁵⁰, R⁵⁷ and R⁵⁸ are as defined and X is chlorine, bromine or iodine.

The substituted aromatic halide is allowed to react with magnesium in a solvent such as ether. The solution is then poured over crushed dry ice and the benzoic acid is isolated by conventional techniques.

The following example teachs the synthesis of a representative compound of Embodiments F and F' of this invention.

EXAMPLE 1-F,F' 2-(4'-Bromo-2'-trifluoromethylbenzoyl)-4,4,6-trimethyl-1,3-cyclohexanedione ##STR69##

4-Bromo-2-trifluoromethylbenzoyl chloride (4.3 g, 15 mmol) and 4,4,6-trimethyl-1,3-cyclohexanedione (2.3 g, 15 mmol) were dissolved in 100 ml methylene chloride. The solution was cooled with an ice bath and triethylamine (2.1 ml, 15 mmol) in 10 ml methylene chloride was added dropwise. The ice bath was then removed and the resulting solution stirred for 30 minutes at room temperature. The solution was washed with 2N hydrochloric acid (2N HCl), 5% potassium carbonate solution (5% K₂ CO₃) and saturated sodium chloride solution (brine), dried over anhydrous magnesium sulfate (MgSO₄) and concentrated under vacuum. The residue (5.1 g) was dissolved in 20 ml acetonitrile. Triethylamine (3.5 ml, 25 mmol) and 0.4 ml acetone cyanohydrin were added and the solution stirred for two hours at room temperature while protected by a drying tube (calcium sulfate). After dilution with ether, the solution was washed with 2N HCl and extracted with 5% K₂ CO₃. The aqueous extract was acidified with concentrated hydrochloric acid and extracted with ether. The ether was washed with brine, dried (MgSO₄) and concentrated under vacuum. The resulting oil was purified on a silica gel column (80:20:1 hexane:ethyl acetate: acetic acid-eluent), yielding 1.5 g of a viscous oil which was identified as the desired compound by nuclear magnetic resonance spectroscopy, infrared spectroscopy and mass spectroscopy.

The compounds of Embodiment G and G' of the present invention can be prepared by the following two-step general method.

The process proceeds via the production of an enol ester intermediate as shown in reaction (1). The final product is obtained by rearrangement of the enol ester as shown in reaction (2). The two reactions may be conducted as separate steps by isolation and recovery of the enol ester using conventional techniques prior to conducting step (2), or by addition of a cyanide source to the reaction medium after the formation of the enol ester, or in one step by inclusion of the cyanide source at the start of reaction (1). ##STR70## wherein R⁶⁰ through R⁶⁶ and moderate base are as defined and X is halogen, preferably chlorine, C₁ -C₄ alkyl-C(O)--O--, C₁ -C₄ alkoxy-C(O)--O-- or ##STR71## wherein R⁶⁰, R⁶⁵ and R⁶⁶ in this portion of the molecule are identical with those in the reactant shown above and the moderate base is as defined, preferably tri-C₁ -C₆ alkylamine alkali metal carbonate or alkali metal phosphate.

Generally, in step (1) mole amounts of the trione and substituted benzoyl reactant are used, along with a mole amount or excess of the base. The two reactants are combined in an organic solvent such as methylene chloride, toluene, ethyl acetate or dimethylformamide. The base or benzoyl reactant preferably is added to the reaction mixture with cooling. The mixture is stirred at 0° C.-50° C. until the reaction is substantially complete. ##STR72## wherein the moderate base and R⁶⁰ through R⁶⁶ are defined above.

Generally, in step (2) a mole of the enol ester intermediate is reacted with 1 to 4 moles of the moderate base, preferably about 2 moles of moderate base and from 0.01 mole to about 0.5 mole or higher, preferably about 0.1 mole of the cyanide source (e.g., potassium cyanide or acetone cyanohydrin). The mixture is stirred in a reaction pot until the rearrangment is substantially complete at a temperature below 50° C., preferably about 20° C. to about 40° C., and the desired product is recovered by conventional techniques.

The term "cyanide source" refers to a substance or substances which under the rearrangement conditions consists of or generates hydrogen cyanide and/or cyanide anion.

The process is conducted in the presence of a catalytic amount of a source of cyanide anion and/or hydrogen cyanide, together with a molar excess, with respect to the enol ester, of a moderate base.

Preferred cyanide sources are alkali metal cyanides such as sodium and potassium cyanide; cyanohydrins of methyl alkyl ketones having from 1-4 carbon atoms in the alkyl groups, such as acetone or methyl isobutyl ketone cyanohydrins; cyanohydrins of benzaldehyde or of C₂ -C₅ aliphatic aldehydes such as acetaldehyde, propionaldehyde, etc., cyanohydrins; zinc cyanide; tri(lower alkyl) silyl cyanides, notably trimethyl silyl cyanide; and hydrogen cyanide itself. Hydrogen cyanide is considered most advantageous as it produces relatively rapid reaction and is inexpensive. Among cyanohydrins the preferred cyanide source is acetone cyanohydrin.

The cyanide source is used in an amount up to about 50 mole percent based on the enol ester. It may be used in as little as about 1 mole percent to produce an acceptable rate of reaction at about 40° C. on a small scale. Larger scale reactions give more reproducible results with slightly higher catalyst levels of about 2 mole percent. Generally about 1-10 mole % of the cyanide source is preferred.

The process is conducted with a molar excess, with respect to the enol ester, of a moderate base. By the term "moderate base" is meant a substance which acts as a base yet whose strength or activity as a base lies between that of strong bases such as hydroxides (which could cause hydrolysis of the enol ester) and that of weak bases such as bicarbonates (which would not function effectively). Moderate bases suitable for use in this embodiment include both organic bases, e.g., trialkylamines such as triethylamine and inorganic bases such as alkali metal carbonates and phosphates. Suitable inorganic bases include potassium carbonate and trisodium phosphate.

The base is used in an amount of from about 1 to about 4 moles per mole of enol ester, preferably about 2 moles per mole.

When the cyanide source is an alkali metal cyanide, particularly potassium cyanide, a phase transfer catalyst may be included in the reaction. Particularly suitable phase transfer catalysts are the crown ethers.

A number of different solvents are useful in this process, depending on the nature of the acid halide or the acylated porduct. A preferred solvent for this reaction is 1,2-dichloroethane. Other solvents which may be employed, depending on the reactants or products include toluene, acetonitrile, methylene chloride, ethyl acetate, dimethylformamide, and methyl isobutyl ketone (MIBK).

In general, depending on the nature of the reactants and the cyanide source, the rearrangement may be conducted at temperatures up to about 50° C.

The above described substituted benzoyl chlorides can be prepared from the corresponding substituted benzoic acids according to the teaching of Reagents for Organic Synthesis, Vol. I, L. F. Fieser and M. Fieser, pp. 767-769 (1967). ##STR73## wherein R⁶⁰, R⁶⁵ and R⁶⁶ are as previously defined.

The substituted benzoic acids can be prepared by a wide variety of general methods according to the teaching of The Chemistry of Carboxylic Acids and Esters, S. Patai, editor, J. Wiley and Sons, New York, N.Y. (1969) and Survey of Organic Synthesis, C. A. Buehler and D. F. Pearson, J. Wiley and Sons, (1970).

The following are three representative examples of the methods described therein. ##STR74## wherein R⁶⁰, R⁶⁵ and R⁶⁶ are as previously defined.

In reaction (a) the substituted benzonitrile is heated to reflux in aqueous sulfuric acid for several hours. The mixture is cooled and the reaction product is isolated by conventional techniques. ##STR75## wherein R⁶⁰, R⁶⁵ and R⁶⁶ are as previously defined.

In reaction (b) the substituted acetophenone is heated to reflux for several hours in an aqueous hypochlorite solution. The mixture is cooled and the reaction product is isolated by conventional techniques. ##STR76## wherein R⁶⁰, R⁶⁵ and R⁶⁶ are as previously defined.

In reaction (c) the substituted toluene is heated to reflux in an aqueous solution of potassium permanganate for several hours. The solution is then filtered and the reaction product is isolated by conventional techniques.

The following example teaches the synthesis of a representative compound of Embodiment G and G' of this invention.

EXAMPLE 1-G,G' 2-(2'-Nitro-4'-chlorobenzoyl)-4,4,6,6-tetramethyl-1,3,5-cyclohexanetrione ##STR77##

2-Nitro-4-chlorobenzoyl chloride (2.2 g, 10 mmol) and 4,4,6,6-tetramethyl-1,3,5-cyclohexanetrione (1.8 g, 10 mmol) were dissolved in methylene chloride. Triethylamine was added and the resulting solution stirred at room temperature for 30 minutes. The solution was washed with 1 normal hydrochloric acid (1N HCl), and saturated sodium chloride (brine), dried over anhydrous magnesium sulfate (MgSO₄) and concentrated under vacuum. The residue was dissolved in 20 ml acetonitrile. Triethylamine (5 ml, 3.5 equivalents) and acetone cyanohydrin (0.5 g, 0.6 equivalent) were added and the mixture stirred at room temperature for 4 hours. After dilution with ether, the solution was washed with 1N HCl and extracted with 5% K₂ CO₃. The basic extract was acidified with HCl and extracted with ether. The ether extract was washed with brine, dried over MgSO₄ and concentrated under vacuum, yielding 2.2 g of crude product. This was recrystallized from benzene to remove syncarpic acid still present. Concentration of the mother liquor under vacuum gave 1.7 g of the desired product as an oil, which solidifed on standing (m.p. 76°-82° C.). It was identified as such by nuclear magnetic resonance spectroscopy, infrared spectroscopy and mass spectroscopy.

The following are tables of certain selected compounds of Embodiments A-G' that are preparable according to the procedures described herein. Compound numbers are assigned to each compound and are used throughout the remainder of the application.

                                      TABLE I-A                                    __________________________________________________________________________      ##STR78##                                                                     Cmpd.                                         n.sub.D.sup.30 or                No. R         R.sup.1                                                                           R.sup.2                                                                            R.sup.3    R.sup.4  R.sup.5                                                                             m.p. °C.                  __________________________________________________________________________     1A  CH.sub.3  CH.sub.3                                                                          Cl  H          H        H    1.5613                           2A  CH.sub.3  CH.sub.3                                                                          Cl  H          4-Cl     H    1.5655                           3A  CH.sub.3  CH.sub.3                                                                          Cl  H          H        6-Cl 103-108                          4A* H         H  Cl  H          4-Cl     H    138-140                          5A  CH.sub.3  CH.sub.3                                                                          Br  H          H        H                                     6A  CH.sub.3  CH.sub.3                                                                          Cl  H          H        5-Cl 74-77                            7A  H         H  Cl  H          H        5-Cl 104-107                          8A  H         H  Br  H          H        H    93-96                            9A  H         H  Cl  H          H        H    79-87                            10A H         H  I   H          H        H    66-70                            11A H         H  Cl  H          4-NO.sub.2                                                                              H    118-122                          12A H         H  Cl  H          H        6-Cl 143-148                          13A H         H  Cl  H          H        5-Br 109-115                          14A H         H  I   3-I        H        5-I  164-167                          15A H         H  Cl  H          H        5-CH.sub.3                                                                          60-65                            16A H         H  Cl  H          4-CH.sub.3                                                                              H    79-86                            17A H         H  Cl  H          4-CH.sub.3 O                                                                            H    60-63                            18A H         H  Cl  3-Cl       H        6-Cl                                  19A H         H  Cl  H          H        5-CH.sub.3 O                                                                        77-80                            20A H         H  Cl  3-Cl       H        H    80-90                            21A H         H  Cl  H          H        5-CF.sub.3                                                                          74-75                            22A H         H  Cl  H          H        5-NO.sub.2                                                                          140-143                          23A H         H  Cl  3-Cl       4-Cl     H    152-154                          24A H         H  Cl  3-Cl       4-CH.sub.3 O                                                                            H    169-170                          25A H         H  Cl  H          4-Br     H    104-107                          26A CH.sub.3  CH.sub.3                                                                          CH.sub.3 O                                                                         H          H        H    104-108                          27A H         H  Cl  H                                                                                          ##STR79##                                                                              H                                     28A H         H  Br  H          H        (a)                                   29A H         H  CH.sub.3 O                                                                         3-CH.sub.3 O                                                                              H        H    75-79                            30A H         H  CH.sub.3 O                                                                         H          H        5-CH.sub.3 O                                                                        89-92                            31A H         H  Br  H          4-CH.sub.3 O                                                                            5-CH.sub.3 O                                                                        92-96                            32A H         H  Br  H          (4)-OCH.sub.2 O-(5)                                                                          63-68                            33A CH.sub.3  CH.sub.3                                                                          Cl  3-Cl       4-Cl     H    86-89                            34A H         H  Cl  3-Cl       H        5-Cl                                  35A CH.sub.3  CH.sub.3                                                                          Cl  3-Cl       H        5-Cl 105-109                          36A CH.sub.3  CH.sub.3                                                                          Cl  3-Cl       4-Cl     5-Cl 137-139                          37A H         H  Cl  3-Cl       4-Cl     5-Cl 106-110                          38A H         H  Cl  H          4-Cl     5-Cl 108-111                          39A                                                                                 ##STR80##                                                                               H  Cl  H          4-Cl     H                                     40A                                                                                 ##STR81##                                                                               H  Cl  H          4-Cl     H                                     41A CH(CH.sub.3).sub.2                                                                       H  Cl  H          4-Cl     H                                     42A CH(CH.sub.3).sub.2                                                                       H  Cl  3-Cl       4-Cl     H                                     43A H         H  Cl  H          4-F      H                                     44A Sodium salt of Compound No. 23            85-94                            45A isopropylamine salt of Compound No. 23    160-165                          46A triethylamine salt of Compound No. 23     82-85                            47A potassium salt of Compound No. 23         107-106                          48A triethanolammonium salt of Compound No. 39                                 49A sodium salt of Compound No. 43            60-63                            50A CH(CH.sub.3).sub.2                                                                       H  Cl  3-CH.sub.3 O                                                                              4-Br     H                                     51A H         H  Cl  H          4-CH.sub.3 SO.sub.2                                                                     H    140-141                          52A H         CH.sub.3                                                                          Cl  H          4-Cl     H                                     53A i-C.sub.4 H.sub.9                                                                        H  Cl  H          4-Cl     H                                     54A i-C.sub.3 H.sub.7                                                                        H  Cl  3-CH.sub.3 O                                                                              H        H                                     55A CH.sub.3  CH.sub.3                                                                          Cl  H          4-CH.sub.3 SO.sub.2                                                                     H                                     56A CH.sub.3  CH.sub.3                                                                          Cl  3-CH.sub.3 4-Cl     H                                     57A H         H  Cl  3-CH.sub.3 4-Cl     H    56-64                            58A H         H  Cl  H          4-C.sub.2 H.sub.5 SO.sub.2                                                              H     98-102                          59A H         H  Cl  3-Cl       4-C.sub.2 H.sub.5 SO.sub.2                                                              H     98-109                          60A H         H  Cl  H          4-C.sub.3 H.sub.7 SO.sub.2                                                              H    semi-solid                       61A H         H  Cl  3-CH.sub.3 O                                                                              4-CH.sub.3 SO.sub.2                                                                     H    48-59                            62A CH.sub.3  CH.sub.3                                                                          Cl  H          4-n-C.sub.3 H.sub.7 SO.sub.2                                                            H    semi-solid                       63A H         H  Cl  3-Cl       4-n-C.sub.3 H.sub.7 SO.sub.2                                                            H      145-148.5                      64A H         H  Cl  3-C.sub.2 H.sub.5 S                                                                       4-C.sub.2 H.sub.5 SO.sub.2                                                              H    oil                              65A CH.sub.3  CH.sub.3                                                                          Cl  H          4-C.sub.2 H.sub.5 SO.sub.2                                                              H    103-108                          66A CH.sub.3  CH.sub.3                                                                          Cl  3-Cl       4-C.sub.2 H.sub.5 SO.sub.2                                                              H    108-114                          67A i-C.sub.3 H.sub.7                                                                        H  Cl  H          4-C.sub.2 H.sub.5 SO.sub.2                                                              H    brown gum                        68A H         H  Cl  3-Cl       4-CH.sub.3 SO.sub.2                                                                     H    145-154                          69A i-C.sub.3 H.sub.7                                                                        H  Cl  3-Cl       4-CH.sub.3 SO.sub.2                                                                     H                                     70A H         H  Br  H          4-CH.sub.3 SO.sub.2                                                                     H    brown gum                        71A H         H  Cl  H          4-i-C.sub.3 H.sub.7 SO.sub.2                                                            H    semi-solid                       72A H         H  Cl  H          4-CH.sub.3 S                                                                            H    74-77                            73A H         H  Cl  3-Cl       4-CH.sub.3 S                                                                            H                                     74A CH.sub.3  CH.sub.3                                                                          Cl  3-Cl       4-n-C.sub.3 H.sub.7 SO.sub.2                                                            H    120-123                          75A H         H  Cl  H          4-n-C.sub.4 H.sub.9 SO.sub.2                                                            H    semi-solid                       76A CH.sub.3  CH.sub.3                                                                          Cl  H          4-n-C.sub.4 H.sub.9 SO.sub.2                                                            H                                     77A H         H  Cl  3-C.sub.2 H.sub.5 O                                                                       4-CH.sub.3 SO.sub.2                                                                     H    semi-solid                       78A H         H  Cl  3-CH.sub.3 O                                                                              4-n-C.sub.3 H.sub.7 SO.sub.2                                                            H    golden gum                       79A CH.sub.3  CH.sub.3                                                                          Cl  H          4-i-C.sub.3 H.sub.7 SO.sub.2                                                            H    125-128                          80A CH(CH.sub.3).sub.2                                                                       H  CH.sub.3 O                                                                         3-Cl       5-Cl     H                                     81A H         H  Cl  3-CH.sub.3 O                                                                              4-Br     H    101-111                          82A H         H  Cl  3-CH.sub.3 4-Cl     H    56-64                            83A H         H  Cl  H          4-Cl     5-CH.sub.3 O                                                                        softens >70                      84A CH(CH.sub.3).sub.2                                                                       H  Cl  3-n-C.sub.3 H.sub.7 O                                                                     4-Br     H                                     85A H         H  Cl  3-C.sub.2 H.sub.5 O                                                                       4-Br     H    101-104                          86A H         H  Cl  H          4-i-C.sub.4 H.sub.9 SO.sub.2                                                            H    136-140                          87A CH.sub.3  CH.sub.3                                                                          Cl  H          4-i-C.sub.4 H.sub.9 SO.sub.2                                                            H                                     88A H         H  Cl  3-Cl       4-i-C.sub.3 H.sub.7 SO.sub.2                                                            H    173-176                          89A H         H  Cl  3-Cl       4-n-C.sub.4 H.sub.9 SO.sub.2                                                            H    135-138                          90A H         H  Cl  3-C.sub.2 H.sub.5 O                                                                       4-C.sub.2 H.sub.5 SO.sub.2                                                              H    gum                              91A H         H  Cl  3-CH.sub.3 O                                                                              4-C.sub.2 H.sub.5 SO.sub.2                                                              H    gum                              92A H         H  Cl  3-Cl       4-C.sub.2 H.sub.5 S                                                                     H    91-94                            93A H         H  Cl  3-C.sub.2 H.sub.5 S                                                                       4-n-C.sub.3 H.sub.7 SO.sub.2                                                            H    oil                              94A H         H  Cl  3-C.sub.2 H.sub.5 S                                                                       4-C.sub.2 H.sub.5 S                                                                     H    oil                              95A H         H  Cl  H          4-(CH.sub.3).sub.2 NSO.sub.2                                                            H    oil                              96A H         H  Cl  3-C.sub.2 H.sub.5 O                                                                       4-n-C.sub.3 H.sub.7 SO.sub.2                                                            H                                     97A H         H  Cl  3-n-C.sub.3 H.sub.7 O                                                                     4-C.sub.2 H.sub.5 SO.sub.2                                                              H    oil                              98A CH.sub.3  CH.sub.3                                                                          Cl  H          4-(CH.sub.3).sub.2 NSO.sub.2                                                            H    oil                              99A H         H  Cl  H          4-(C.sub.2 H.sub.5).sub.2 NSO.sub.2                                                     H    90-92                            100A                                                                               CH.sub.3  CH.sub.3                                                                          Cl  H          4-(C.sub.2 H.sub.5).sub.2 NSO.sub.2                                                     H                                     101A                                                                               H         H  Cl  H          4-C.sub.2 H.sub.5 S                                                                     H                                     102A                                                                               H         H  Cl  H          4-n-C.sub.3 H.sub.7 S                                                                   H                                     103A                                                                               H         H  Cl  H          4-i-C.sub.3 H.sub.7 S                                                                   H                                     104A                                                                               H         H  Cl  H          4-C.sub.2 H.sub.5 SO                                                                    H                                     105A                                                                               H         H  CH.sub.3 O                                                                         H          4-NO.sub.2                                                                              H    semi-solid                       106A                                                                               H         H  Cl  3-n-C.sub.3 H.sub.7 O                                                                     4-Br     H                                     107A                                                                               H         H  Cl  3-n-C.sub.3 H.sub.7 O                                                                     4-CH.sub.3 SO.sub.2                                                                     H     96-100                          108A                                                                               H         H  Cl  3-allyloxy 4-CH.sub.3 SO.sub.2                                                                     H    semi-solid                       109A                                                                               H         H  Cl  3-CH.sub.3 C(O)NH                                                                         4-Cl     H    155-160                          110A                                                                               H         H  Cl  3-Cl       4-n-C.sub.3 H.sub.7 S                                                                   H                                     111A                                                                               H         H  Cl  3-CH.sub.3 O                                                                              4-NO.sub.2                                                                              H    150-153                          112A                                                                               H         H  Cl  3-allyloxy 4-C.sub.2 H.sub.5 SO.sub.2                                                              H                                     113A                                                                               H         H  Cl  3-CH.sub.2 BrCHBrCH.sub.2 O                                                               4-C.sub.2 H.sub.5 SO.sub.2                                                              H                                     114A                                                                               H         H  Cl  3-n-C.sub.4 H.sub.9 O                                                                     4-C.sub.2 H.sub.5 SO.sub.2                                                              H    gum                              115A                                                                               H         H  Cl  3-i-C.sub.4 H.sub.9 O                                                                     4-C.sub.2 H.sub.5 SO.sub.2                                                              H                                     116A                                                                               H         H  Cl  H          4-allylthio                                                                             H                                     117A                                                                               CH.sub.3  CH.sub.3                                                                          Cl  H          4-NO.sub.2                                                                              H                                     118A                                                                               H         H  Cl  3-CH.sub.3 C(O)N(CH.sub.3)                                                                4-Cl     H                                     119A                                                                               H         H  Cl  3-i-C.sub.3 H.sub.7 O                                                                     4-C.sub.2 H.sub.5 SO.sub.2                                                              H                                     120A                                                                               H         H  Cl  3-CH.sub.2 ClCH.sub.2 CH.sub.2 O                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                              H    gum                              121A                                                                               H         H  Cl  H          4-t-C.sub.4 H.sub.9 S                                                                   H                                     122A                                                                               H         H  Cl  3-CH.sub.3 O                                                                              4-CH.sub.2 H.sub.5 S                                                                    H                                     123A                                                                               H         H  Cl  H          4-CF.sub.3                                                                              H                                     124A                                                                               H         H  Cl  H          4-Cl     6-Cl                                  125A                                                                               H         H  Cl  3-CH.sub.3 C(O)N(CH.sub.3)                                                                H        H    131-135                          126A                                                                               H         H  Cl  3-CH.sub.3 C(O)NH                                                                         H        H                                     127A                                                                               H         H  Cl  3-(CH.sub.3).sub.2 N                                                                      4-Cl     H                                     128A                                                                               CH.sub.3  H  Cl  3-CH.sub.3 O                                                                              4-CH.sub.3 SO.sub.2                                                                     H    117-122                          129A                                                                               H         H  Cl  H          4-C.sub.2 H.sub.5 SO.sub.2                                                              H                                     130A                                                                               H         H  Br  H          H        H                                     131A                                                                               H         H  Br  H          4-C.sub.2 H.sub.5 OC(O)                                                                 H                                     132A                                                                               H         H  Cl  H          4-CN     H    183-184                          133A                                                                               H         H  Cl  3-CH.sub.3 C(O)NH                                                                         H        6-NO.sub.2                            134A                                                                               H         H  Cl  3-(CH.sub.3).sub.2 N                                                                      H        H                                     135A                                                                               H         H  Cl  3-Cl       4-ClCH.sub.2 CH.sub.2 SO.sub.2                                                          H                                     __________________________________________________________________________      *Prepared in Exampel 1A.                                                       ##STR82##                                                                

                                      TABLE I-B                                    __________________________________________________________________________      ##STR83##                                                                     Compound                                                                       Number                                                                               R.sup.10 R.sup.11                                                                           R.sup.12                                                                           R.sup.13                                                                             R.sup.14  R.sup.15                                                                          R.sup.16                                                                          R.sup.17                                                                          R.sup.18                       __________________________________________________________________________      1B                                                                                   ##STR84##                                                                              H   Cl  H     4-Cl      H  H  H  H                               2B                                                                                   ##STR85##                                                                              CH.sub.3                                                                           Cl  H     4-Cl      H  H  H  H                               3B   triethanolammonium salt of Compound No. 2                                 4B   triethanolammonium salt of Compound No. 7                                 5B                                                                                   ##STR86##                                                                              CH.sub.3                                                                           Cl  3-Cl  4-Cl      H  H  H  H                               6B   triethanolammonium salt of compound No. 5                                 7B.sup.a                                                                            CH.sub.3 CH.sub.3                                                                           Cl  H     4-Cl      H  H  H  H                               8B   CH.sub.3 CH.sub.3                                                                           Cl  H     4-Cl      CH.sub.3                                                                          H  H  H                               9B   CH.sub.3 n-C.sub.3 H.sub.7                                                                  Cl  H     4-Cl      H  H  H  H                              10B   CH.sub.3 H   Cl  H     4-Cl      H  H  H  H                              11B   CH.sub.3 H   Cl  H     4-Cl      CH.sub.3                                                                          H  H  H                              12B   C.sub.5 H.sub.10                                                                            Cl  H     4-Cl      H  H  H  H                              13B   CH.sub.3 CH.sub.3                                                                           Cl  3-Cl  4-Cl      H  H  H  H                              14B   CH.sub.3 CH.sub.3                                                                           Cl  3-Cl  4-Cl      CH.sub.3                                                                          H  H  H                              15B   i-C.sub.3 H.sub.7                                                                       H   Cl  3-Cl  4-Cl      H  H  H  H                              16B   CH.sub.3 CH.sub. 3                                                                          Cl  H     4-CH.sub.3 SO.sub.2                                                                      H  H  H  H                              17B   CH.sub.3 CH.sub.3                                                                           Cl  H     4-CH.sub.3 SO.sub.2                                                                      CH.sub.3                                                                          H  H  H                              18B   CH.sub.3 H   Cl  H     4-CH.sub.3 SO.sub.2                                                                      H  H  H  H                              19B   CH.sub.3 CH.sub.3                                                                           Cl  3-Cl  4-CH.sub.3 SO.sub.2                                                                      H  H  H  H                              20B   CH.sub.3 CH.sub.3                                                                           Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                                                               H  H  H  H                              21B   CH.sub.3 CH.sub.3                                                                           Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                               H  H  H  H                              22B   CH.sub.3 CH.sub.3                                                                           Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                               CH.sub.3                                                                          H  H  H                              23B   CH.sub.3 CH.sub.3                                                                           Cl  3-OCH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                               H  H  H  H                              24B   CH.sub.3 CH.sub.3                                                                           Cl  3-OCH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                      H  H  H  H                              25B   CH.sub.3 CH.sub.3                                                                           Cl  3-CH.sub.3                                                                           4-Cl      H  H  H  H                              26B   CH.sub.3 CH.sub.3                                                                           Cl  3-OCH.sub.3                                                                          4-Cl      H  H  H  H                              27B   CH.sub.3 C.sub.2 H.sub.5                                                                    Cl  H     4-Cl      H  H  H  H                              28B   CH.sub.3 CH.sub.3                                                                           Cl  H     H         H  H  H  H                              29B   CH.sub.3 CH.sub.3                                                                           Cl  3-OCH.sub.3                                                                          4-Br      H  H  H  H                              30B   CH.sub.3 CH.sub.3                                                                           Cl  H     4-Br      H  H  H  H                              31B   CH.sub.3 C.sub.2 H.sub.5                                                                    Cl  3-Cl  4-Cl      H  H  H  H                              32B   n-C.sub.3 H.sub.7                                                                       H   Cl  H     4-Cl      H  H  H  H                              33B                                                                                   ##STR87##                                                                              n-C.sub.3 H.sub.7                                                                  Cl  H     4-Cl      H  H  H  H                              34B   CH.sub.3 CH.sub.3                                                                           Cl  H     4-i-C.sub.3 H.sub.7 SO.sub.2                                                             H  H  H  H                              35B   CH.sub.3 CH.sub.3                                                                           Cl  3-i-C.sub.3 H.sub.7 O                                                                4-Br      H  H  H  H                              36B   CH.sub.3 CH.sub.3                                                                           Cl  H     6-F       H  H  H  H                              37B   i-C.sub.3 H.sub.7                                                                       H   Cl  3-Cl  4-Cl      H  H  H  H                              38B   CH.sub.3 CH.sub.3                                                                           Cl  3-OC.sub.2 H.sub.5                                                                   4-Br      CH.sub.3                                                                          H  H  H                              39B   i-C.sub.3 H.sub.7 OC(O)                                                                 H   Cl  H     4-Cl      H  H  H  H                              40B   C.sub.2 H.sub.5 OC(O)                                                                   n-C.sub.3 H.sub.7                                                                  Cl  H     4-Cl      H  H  H  H                              41B   C.sub.5 H.sub.10                                                                            Cl  H     4-Cl      H  H  H  H                              42B   CH.sub.3 CH.sub.3                                                                           Cl  H     4-Cl      H  H  CH.sub.3                                                                          H                              43B   CH.sub.3 CH.sub.3                                                                           Cl  H     4-n-C.sub.3 H.sub.7 SO.sub.2                                                             H  H  H  H                              44B   CH.sub.3 CH.sub.3                                                                           Cl  3-Cl  4-n-C.sub.3 H.sub.7 SO.sub.2                                                             H  H  H  H                              45B   CH.sub.3 CH.sub.3                                                                           CH.sub.3 O                                                                         3-CH.sub.3 O                                                                         H         H  H  H  H                              46B   CH.sub.3 CH.sub.3                                                                           CH.sub.3 O                                                                         H     4-Cl      H  H  H  H                              47B   CH.sub.3 CH.sub.3                                                                           Cl  H     4-Br      CH.sub.3                                                                          H  H  H                              48B   CH.sub.3 CH.sub.3                                                                           Br  H     H         H  H  H  H                              49B   CH.sub.3 CH.sub.3                                                                           I   H     H         H  H  H  H                              50B   CH.sub.3 CH.sub.3                                                                           F   H     H         H  H  H  H                              51B   CH.sub.3 CH.sub.3                                                                           CH.sub.3 O                                                                         H     H         H  H  H  H                              52B   CH.sub.3 CH.sub.3                                                                           Cl  3-allyoxy                                                                            4-Br      H  H  H  H                              53B   CH.sub.3 CH.sub.3                                                                           Cl  H     4-CH.sub.3 SO.sub.2                                                                      H  H  CH.sub.3                                                                          H                              54B   CH.sub.3 CH.sub.3                                                                           Cl  3-CH.sub.3 O                                                                         4-Br      CH.sub.3                                                                          H  H  H                              55B   CH.sub.3 CH.sub.3                                                                           Br  H     4-CN      H  H  H  H                              56B   CH.sub.3 CH.sub.3                                                                           Cl  H     4N(CH.sub.3)SO.sub.2 CF.sub.3                                                            H  H  H  H                              57B   CH.sub.3 CH.sub.3                                                                           Cl  3-NO.sub.2                                                                           H         H  H  H  H                              58B   CH.sub.3 CH.sub.3                                                                           C.sub.2 H.sub.5 O                                                                  H     4-Cl      H  H  H  H                              59B   CH.sub.3 CH.sub.3                                                                           Cl  H     4-i-C.sub.4 H.sub.9 SO.sub.2                                                             H  H  H  H                              60B   CH.sub.3 CH.sub.3                                                                           Cl  3-C.sub.2 H.sub.5 O                                                                  4-CH.sub.3 SO.sub.2                                                                      H  H  H  H                              61B   CH.sub.3 CH.sub.3                                                                           Cl  3-CH.sub.3 O                                                                         4-C.sub.2 H.sub.5 SO.sub.2                                                               H  H  H  H                              62B   CH.sub.3 CH.sub.3                                                                           Cl  H     4-n-C.sub.4 H.sub.9 SO.sub.2                                                             H  H  H  H                              63B   CH.sub.3 CH.sub.3                                                                           Cl  3-Cl  4-n-C.sub.4 H.sub.9 SO.sub.2                                                             CH.sub.3                                                                          H  H  H                              64B   CH.sub.3 CH.sub.3                                                                           Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                                                               CH.sub.3                                                                          H  H  H                              65B   CH.sub.3 CH.sub.3                                                                           Cl  H     4-F       H  H  H  H                              66B   CH.sub.3 H   Cl  3-CH.sub.3 O                                                                         4-Br      H  H  H  H                              67B   CH.sub.3 CH.sub.3                                                                           Cl  3-CH.sub.3 O                                                                         H         H  H  H  H                              68B   CH.sub. 3                                                                               CH.sub.3                                                                           Cl  3-C.sub.2 H.sub.5 S                                                                  4-n-C.sub.3 H.sub.7 SO.sub.2                                                             H  H  H  H                              69B   CH.sub.3 CH.sub.3                                                                           Cl  3-C.sub.2 H.sub.5 S                                                                  4-C.sub.2 H.sub.5 S                                                                      H  H  H  H                              70B   CH.sub.3 CH.sub.3                                                                           Cl  3-C.sub.2 H.sub.5                                                                    4-C.sub.2 H.sub.5 SO.sub.2                                                               H  H  H  H                              71B   CH.sub.3 CH.sub.3                                                                           Cl  3-C.sub.2 H.sub.5 S                                                                  4-CH.sub.3 SO.sub.2                                                                      H  H  H  H                              72B   CH.sub.3 CH.sub.3                                                                           Cl  Cl    4-i-C.sub.3 H.sub.7 SO.sub.2                                                             H  H  H  H                              73B   CH.sub.3 CH.sub.3                                                                           Cl  3-Cl  4-n-C.sub.4 H.sub.9 SO.sub.2                                                             H  H  H  H                              74B   CH.sub.3 CH.sub.3                                                                           Cl  3-C.sub.2 H.sub.5 O                                                                  4-C.sub.2 H.sub.5 SO.sub.2                                                               H  H  H  H                              75B   CH.sub.3 CH.sub.3                                                                           Cl  3-C.sub.2 H.sub.5 O                                                                  4-Br      H  H  H  H                              76B   CH.sub.3 CH.sub.3                                                                           Cl  3-C.sub.2 H.sub.5 O                                                                  4-n-C.sub.3 H.sub.7 SO.sub.2                                                             H  H  H  H                              77B   CH.sub.3 CH.sub.3                                                                           Cl  3-n-C.sub.3 H.sub.7 O                                                                4-C.sub.2 H.sub.5 SO.sub.2                                                               H  H  H  H                              78B   CH.sub.3 CH.sub.3                                                                           Cl  H     4-(CH.sub.3 ).sub.2 NSO.sub.2                                                            H  H  H  H                              79B   CH.sub.3 CH.sub.3                                                                           Cl  3-CH.sub.3 S                                                                         4-C.sub.2 H.sub.5 SO.sub.2                                                               H  H  H  H                              80B   CH.sub.3 CH.sub.3                                                                           Cl  3-Cl  4-C.sub.2 H.sub.5 S                                                                      H  H  H  H                              81B   CH.sub.3 CH.sub.3                                                                           Cl  H     4-C.sub.2 H.sub.5 S                                                                      H  H  H  H                              82B   CH.sub.3 CH.sub.3                                                                           Cl  H     4-(C.sub.2 H.sub.5).sub.2 NSO.sub.2                                                      H  H  H  H                              83B   CH.sub.3 CH.sub.3                                                                           Cl  H     4-n-C.sub.3 H.sub.7 SO.sub.2                                                             H  H  H  H                              84B   CH.sub.3 CH.sub.3                                                                           Cl  H     4-n-C.sub.3 H.sub.7 S                                                                    CH.sub.3                                                                          H  H  H                              85B   CH.sub.3 CH.sub.3                                                                           Cl  H     4-C.sub.2 H.sub.5 S(O)                                                                   H  H  H  H                              86B   CH.sub.3 CH.sub.3                                                                           Cl  H     4-i-C.sub.3 H.sub.7 S                                                                    H  H  H  H                              87B   CH.sub.3 CH.sub.3                                                                           Cl  3-Cl  4-n-C.sub.3 H.sub.7 S                                                                    H  H  H  H                              88B   CH.sub.3 CH.sub.3                                                                           Cl  H     4-t-C.sub.4 H.sub.9 SO.sub.2                                                             H  H  H  H                              89B   CH.sub.3 CH.sub.3                                                                           Cl  H     4-i-C.sub.3 H.sub.7 S                                                                    CH.sub.3                                                                          H  H  H                              90B   CH.sub.3 CH.sub.3                                                                           Cl  H     4-n-C.sub.3 H.sub.7 SO.sub.2                                                             CH.sub.3                                                                          H  H  H                              91B   CH.sub.3 CH.sub.3                                                                           Cl  *     4-Cl      H  H  H  H                              92B   CH.sub.3 CH.sub.3                                                                           Cl  H     4-CH.sub.2CHCH.sub.2 S                                                                   H  H  H  H                              93B   CH.sub.3 CH.sub.3                                                                           Cl  3-C.sub.2 H.sub.5 O                                                                  4-C.sub.2 H.sub.5 S                                                                      H  H  H  H                              94B   CH.sub.3 CH.sub.3                                                                           Cl  3-Cl  4-CH.sub.3 S                                                                             CH.sub.3                                                                          H  H  H                              95B   CH.sub.3 CH.sub.3                                                                           Cl  H     4-CH.sub.3 S                                                                             H  H  H  H                              96B   CH.sub.3 CH.sub.3                                                                           Cl  3-i-C.sub.3 H.sub.7 O                                                                4-C.sub.2 H.sub.5 SO.sub.2                                                               H  H  H  H                              97B   CH.sub.3 CH.sub.3                                                                           Cl  3-CH.sub.3 O                                                                         4-C.sub.2 H.sub.5 S                                                                      H  H  H  H                              98B   CH.sub.3 CH.sub.3                                                                           Cl  **    4-Cl      H  H  H  H                              99B   CH.sub.3 CH.sub.3                                                                           Cl  **    H         H  H  H  H                              100B  CH.sub.3 CH.sub.3                                                                           Cl  3-Cl  4-CH.sub.3 S                                                                             H  H  H  H                              101B  CH.sub.3 CH.sub.3                                                                           CH.sub.3 O                                                                         H     4-NO.sub.2                                                                               H  H  H  H                              102B  CH.sub.3 CH.sub.3                                                                           CH.sub.3 O                                                                         H     4-CF.sub.3                                                                               H  H  H  H                              103B  CH.sub.3 CH.sub.3                                                                           Cl  H     4-n-C.sub.3 H.sub.7 SO                                                                   H  H  H  H                              104B  CH.sub.3 CH.sub.3                                                                           Cl  H     4-n-C.sub.3 H.sub.7 SO                                                                   CH.sub.3                                                                          H  H  H                              __________________________________________________________________________      .sup.a Prepared in Example IB.                                                 * = 3CH.sub.3 C(O)NH                                                           ** = 3CH.sub.3 C(O)N(CH.sub.3)                                           

The following additional compounds can be prepared by the general method hereinbefore taught.

                                      TABLE I-B                                    __________________________________________________________________________      ##STR88##                                                                     R.sup.10                                                                            R.sup.11                                                                            R.sup.12                                                                           R.sup.13                                                                             R.sup.14                                                                              R.sup.15                                                                          R.sup.16                                                                          R.sup.17                                                                          R.sup.18                                   __________________________________________________________________________     CH.sub.3                                                                            n-C.sub.3 H.sub.7                                                                   Cl  H     4-Cl   CH.sub.3                                                                          H  H  H                                          CH.sub.3                                                                            n-C.sub.4 H.sub.9                                                                   Cl  H     4-Cl   H  H  H  H                                          CH.sub.3                                                                            n-C.sub.4 H.sub.9                                                                   Cl  H     4-Cl   CH.sub.3                                                                          H  H  H                                          C.sub.2 H.sub.5                                                                     H    Cl  H     4-Cl   H  H  H  H                                          C.sub.2 H.sub.5                                                                     H    Cl  H     4-Cl   CH.sub.3                                                                          H  H  H                                          n-C.sub.4 H.sub.9                                                                   H    Cl  H     4-Cl   H  H  H  H                                          n-C.sub.4 H.sub.9                                                                   H    Cl  H     4-Cl   CH.sub.3                                                                          H  H  H                                          i-C.sub.3 H.sub.7                                                                   H    Cl  H     4-Cl   H  H  H  H                                          i-C.sub.3 H.sub.7                                                                   H    Cl  H     4-Cl   CH.sub.3                                                                          H  H  H                                          C.sub.5 H.sub.10                                                                         Cl  H     4-Cl   CH.sub.3                                                                          H  H  H                                          CH.sub.3                                                                            n-C.sub.3 H.sub.7                                                                   Cl  3-Cl  4-Cl   H  H  H  H                                          CH.sub.3                                                                            n-C.sub.3 H.sub.7                                                                   Cl  3-Cl  4-Cl   CH.sub.3                                                                          H  H  H                                          CH.sub.3                                                                            n-C.sub.4 H.sub.9                                                                   Cl  3-Cl  4-Cl   H  H  H  H                                          CH.sub.3                                                                            n-C.sub.4 H.sub.9                                                                   Cl  3-Cl  4-Cl   CH.sub.3                                                                          H  H  H                                          CH.sub.3                                                                            H    Cl  3-Cl  4-Cl   H  H  H  H                                          CH.sub.3                                                                            H    Cl  3-Cl  4-Cl   CH.sub.3                                                                          H  H  H                                          C.sub.2 H.sub.5                                                                     H    Cl  3-Cl  4-Cl   H  H  H  H                                          C.sub.2 H.sub.5                                                                     H    Cl  3-Cl  4-Cl   CH.sub.3                                                                          H  H  H                                          n-C.sub.4 H.sub.9                                                                   H    Cl  3-Cl  4-Cl   H  H  H  H                                          n-C.sub.4 H.sub.9                                                                   H    Cl  3-Cl  4-Cl   CH.sub.3                                                                          H  H  H                                          C.sub.5 H.sub.10                                                                         Cl  3-Cl  4-Cl   H  H  H  H                                          C.sub.5 H.sub.10                                                                         Cl  3-Cl  4-Cl   CH.sub.3                                                                          H  H  H                                          CH.sub.3                                                                            n-C.sub.3 H.sub.7                                                                   Cl  H     4-CH.sub.3 SO.sub.2                                                                   H  H  H  H                                          CH.sub.3                                                                            n-C.sub.3 H.sub.7                                                                   Cl  H     4-CH.sub.3 SO.sub.2                                                                   CH.sub.3                                                                          H  H  H                                          CH.sub.3                                                                            n-C.sub.4 H.sub.9                                                                   Cl  H     4-CH.sub.3 SO.sub.2                                                                   H  H  H  H                                          CH.sub.3                                                                            n-C.sub.4 H.sub.9                                                                   Cl  H     4-CH.sub.3 SO.sub.2                                                                   CH.sub.3                                                                          H  H  H                                          CH.sub.3                                                                            H    Cl  H     4-CH.sub.3 SO.sub.2                                                                   CH.sub.3                                                                          H  H  H                                          C.sub.2 H.sub.5                                                                     H    Cl  H     4-CH.sub.3 SO.sub.2                                                                   H  H  H  H                                          C.sub.2 H.sub.5                                                                     H    Cl  H     4-CH.sub.3 SO.sub.2                                                                   CH.sub.3                                                                          H  H  H                                          n-C.sub.4 H.sub.9                                                                   H    Cl  H     4-CH.sub.3 SO.sub.2                                                                   H  H  H  H                                          n-C.sub.4 H.sub.9                                                                   H    Cl  H     4-CH.sub.3 SO.sub.2                                                                   CH.sub.3                                                                          H  H  H                                          i-C.sub.3 H.sub.7                                                                   H    Cl  H     4-CH.sub.3 SO.sub.2                                                                   H  H  H  H                                          i-C.sub.3 H.sub.7                                                                   H    Cl  H     4-CH.sub.3 SO.sub.2                                                                   CH.sub.3                                                                          H  H  H                                          C.sub.5 H.sub.10                                                                         Cl  H     4-CH.sub.3 SO.sub.2                                                                   H  H  H  H                                          C.sub.5 H.sub.10                                                                         Cl  H     4-CH.sub.3 SO.sub.2                                                                   CH.sub.3                                                                          H  H  H                                          CH.sub.3                                                                            n-C.sub.3 H.sub.7                                                                   Cl  3-Cl  4-CH.sub.3 SO.sub.2                                                                   H  H  H  H                                          CH.sub.3                                                                            n-C.sub.3 H.sub.7                                                                   Cl  3-Cl  4-CH.sub.3 SO.sub.2                                                                   CH.sub.3                                                                          H  H  H                                          CH.sub.3                                                                            n-C.sub.4 H.sub.9                                                                   Cl  3-Cl  4-CH.sub.3 SO.sub.2                                                                   H  H  H  H                                          CH.sub.3                                                                            n-C.sub.4 H.sub.9                                                                   Cl  3-Cl  4-CH.sub.3 SO.sub.2                                                                   CH.sub.3                                                                          H  H  H                                          CH.sub.3                                                                            H    Cl  3-Cl  4-CH.sub.3 SO.sub.2                                                                   H  H  H  H                                          CH.sub.3                                                                            H    Cl  3-Cl  4-CH.sub.3 SO.sub.2                                                                   CH.sub.3                                                                          H  H  H                                          C.sub.2 H.sub.5                                                                     H    Cl  3-Cl  4-CH.sub.3 SO.sub.2                                                                   H  H  H  H                                          C.sub.2 H.sub.5                                                                     H    Cl  3-Cl  4-CH.sub.3 SO.sub.2                                                                   CH.sub.3                                                                          H  H  H                                          n-C.sub.4 H.sub.9                                                                   H    Cl  3-Cl  4-CH.sub.3 SO.sub.2                                                                   H  H  H  H                                          n-C.sub.4 H.sub.9                                                                   H    Cl  3-Cl  4-CH.sub.3 SO.sub.2                                                                   CH.sub.3                                                                          H  H  H                                          i-C.sub.3 H.sub.7                                                                   H    Cl  3-Cl  4-CH.sub.3 SO.sub.2                                                                   H  H  H  H                                          i-C.sub.3 H.sub.7                                                                   H    Cl  3-Cl  4-CH.sub.3 SO.sub.2                                                                   CH.sub.3                                                                          H  H  H                                          C.sub.5 H.sub.10                                                                         Cl  3-Cl  4-CH.sub.3 SO.sub.2                                                                   H  H  H  H                                          C.sub.5 H.sub.10                                                                         Cl  3-Cl  4-CH.sub.3 SO.sub.2                                                                   CH.sub.3                                                                          H  H  H                                          CH.sub.3                                                                            n-C.sub.3 H.sub.7                                                                   Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                                                            H  H  H  H                                          CH.sub.3                                                                            n-C.sub.3 H.sub.7                                                                   Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                                                            CH.sub.3                                                                          H  H  H                                          CH.sub.3                                                                            n-C.sub.4 H.sub.9                                                                   Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                                                            H  H  H  H                                          CH.sub.3                                                                            n-C.sub.4 H.sub.9                                                                   Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                                                            CH.sub.3                                                                          H  H  H                                          CH.sub.3                                                                            H    Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                                                            H  H  H  H                                          CH.sub.3                                                                            H    Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                                                            CH.sub.3                                                                          H  H  H                                          C.sub.2 H.sub.5                                                                     H    Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                                                            H  H  H  H                                          C.sub.2 H.sub.5                                                                     H    Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                                                            CH.sub.3                                                                          H  H  H                                          n-C.sub.4 H.sub.9                                                                   H    Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                                                            H  H  H  H                                          n-C.sub.4 H.sub.9                                                                   H    Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                                                            CH.sub.3                                                                          H  H  H                                          i-C.sub.3 H.sub.7                                                                   H    Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                                                            H  H  H  H                                          i-C.sub.3 H.sub.7                                                                   H    Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                                                            CH.sub.3                                                                          H  H  H                                          C.sub.5 H.sub.10                                                                         Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                                                            H  H  H  H                                          C.sub.5 H.sub.10                                                                         Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                                                            CH.sub.3                                                                          H  H  H                                          CH.sub.3                                                                            n-C.sub.3 H.sub.7                                                                   Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                            H  H  H  H                                          CH.sub.3                                                                            n-C.sub.3 H.sub.7                                                                   Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                            CH.sub.3                                                                          H  H  H                                          CH.sub.3                                                                            n-C.sub.4 H.sub.9                                                                   Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                            H  H  H  H                                          CH.sub.3                                                                            n-C.sub.4 H.sub.9                                                                   Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                            CH.sub.3                                                                          H  H  H                                          CH.sub.3                                                                            H    Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                            H  H  H  H                                          CH.sub.3                                                                            H    Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                            CH.sub.3                                                                          H  H  H                                          C.sub.2 H.sub.5                                                                     H    Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                            H  H  H  H                                          C.sub.2 H.sub.5                                                                     H    Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                            CH.sub.3                                                                          H  H  H                                          n-C.sub.4 H.sub.9                                                                   H    Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                            H  H  H  H                                          n-C.sub.4 H.sub.9                                                                   H    Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                            CH.sub.3                                                                          H  H  H                                          i-C.sub.3 H.sub.7                                                                   H    Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                            H  H  H  H                                          i-C.sub.3 H.sub.7                                                                   H    Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                            CH.sub.3                                                                          H  H  H                                          C.sub.5 H.sub.10                                                                         Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                            H  H  H  H                                          C.sub.5 H.sub.10                                                                         Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                            CH.sub.3                                                                          H  H  H                                          CH.sub.3                                                                            CH.sub.3                                                                            Cl  3-OCH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                            CH.sub.3                                                                          H  H  H                                          CH.sub.3                                                                            n-C.sub.3 H.sub.7                                                                   Cl  3-OCH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                            H  H  H  H                                          CH.sub.3                                                                            n-C.sub.3 H.sub.7                                                                   Cl  3-OCH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                            CH.sub.3                                                                          H  H  H                                          CH.sub.3                                                                            n-C.sub.4 H.sub.9                                                                   Cl  3-OCH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                            H  H  H  H                                          CH.sub.3                                                                            n-C.sub.4 H.sub.9                                                                   Cl  3-OCH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                            CH.sub.3                                                                          H  H  H                                          CH.sub.3                                                                            H    Cl  3-OCH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                            H  H  H  H                                          CH.sub.3                                                                            H    Cl  3-OCH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                            CH.sub.3                                                                          H  H  H                                          C.sub.2 H.sub.5                                                                     H    Cl  3-OCH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                            H  H  H  H                                          C.sub.2 H.sub.5                                                                     H    Cl  3-OCH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                            CH.sub.3                                                                          H  H  H                                          n-C.sub.4 H.sub.9                                                                   H    Cl  3-OCH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                            H  H  H  H                                          n-C.sub.4 H.sub.9                                                                   H    Cl  3-OCH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                            CH.sub.3                                                                          H  H  H                                          i-C.sub.3 H.sub.7                                                                   H    Cl  3-OCH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                            H  H  H  H                                          i-C.sub.3 H.sub.7                                                                   H    Cl  3-OCH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                            CH.sub.3                                                                          H  H  H                                          C.sub.5 H.sub.10                                                                         Cl  3-OCH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                            H  H  H  H                                          C.sub.5 H.sub.10                                                                         Cl  3-OCH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                            CH.sub.3                                                                          H  H  H                                          CH.sub.3                                                                            CH.sub.3                                                                            Cl  3-CH.sub.3                                                                           4-C.sub.2 H.sub.5 SO.sub.2                                                            H  H  H  H                                          CH.sub.3                                                                            CH.sub.3                                                                            Cl  3-CH.sub.3                                                                           4-C.sub.2 H.sub.5 SO.sub.2                                                            CH.sub.3                                                                          H  H  H                                          CH.sub.3                                                                            n-C.sub.3 H.sub.7                                                                   Cl  3-CH.sub.3                                                                           4-C.sub.2 H.sub.5 SO.sub.2                                                            H  H  H  H                                          CH.sub.3                                                                            n-C.sub.3 H.sub.7                                                                   Cl  3-CH.sub.3                                                                           4-C.sub.2 H.sub.5 SO.sub.2                                                            CH.sub.3                                                                          H  H  H                                          CH.sub.3                                                                            n-C.sub.4 H.sub.9                                                                   Cl  3-CH.sub.3                                                                           4-C.sub.2 H.sub.5 SO.sub.2                                                            H  H  H  H                                          CH.sub. 3                                                                           n-C.sub.4 H.sub.9                                                                   Cl  3-CH.sub.3                                                                           4-C.sub.2 H.sub.5 SO.sub.2                                                            CH.sub.3                                                                          H  H  H                                          CH.sub.3                                                                            H    Cl  3-CH.sub.3                                                                           4-C.sub.2 H.sub.5 SO.sub.2                                                            H  H  H  H                                          CH.sub.3                                                                            H    Cl  3-CH.sub.3                                                                           4-C.sub.2 H.sub.5 SO.sub.2                                                            CH.sub.3                                                                          H  H  H                                          C.sub.2 H.sub.5                                                                     H    Cl  3-CH.sub.3                                                                           4-C.sub.2 H.sub.5 SO.sub.2                                                            H  H  H  H                                          C.sub.2 H.sub.5                                                                     H    Cl  3-CH.sub.3                                                                           4-C.sub.2 H.sub.5 SO.sub.2                                                            CH.sub.3                                                                          H  H  H                                          n-C.sub.4 H.sub.9                                                                   H    Cl  3-CH.sub.3                                                                           4-C.sub.2 H.sub.5 SO.sub.2                                                            H  H  H  H                                          n-C.sub.4 H.sub.9                                                                   H    Cl  3-CH.sub.3                                                                           4-C.sub.2 H.sub.5 SO.sub.2                                                            CH.sub.3                                                                          H  H  H                                          i-C.sub.3 H.sub.7                                                                   H    Cl  3-CH.sub.3                                                                           4-C.sub.2 H.sub.5 SO.sub.2                                                            H  H  H  H                                          i-C.sub.3 H.sub.7                                                                   H    Cl  3-CH.sub.3                                                                           4-C.sub.2 H.sub.5 SO.sub.2                                                            CH.sub.3                                                                          H  H  H                                          C.sub.5 H.sub.10                                                                         Cl  3-CH.sub.3                                                                           4-C.sub.2 H.sub.5 SO.sub.2                                                            H  H  H  H                                          C.sub.5 H.sub.10                                                                         Cl  3-CH.sub.3                                                                           4-C.sub. 2 H.sub.5 SO.sub.2                                                           CH.sub.3                                                                          H  H  H                                          CH.sub.3                                                                            CH.sub.3                                                                            Cl  3-OCH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                   CH.sub.3                                                                          H  H  H                                          CH.sub.3                                                                            n-C.sub.3 H.sub.7                                                                   Cl  3-OCH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                   H  H  H  H                                          CH.sub.3                                                                            n-C.sub.3 H.sub.7                                                                   Cl  3-OCH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                   CH.sub.3                                                                          H  H  H                                          CH.sub.3                                                                            n-C.sub.4 H.sub.9                                                                   Cl  3-OCH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                   H  H  H  H                                          CH.sub.3                                                                            n-C.sub.4 H.sub.9                                                                   Cl  3-OCH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                   CH.sub.3                                                                          H  H  H                                          CH.sub.3                                                                            H    Cl  3-OCH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                   H  H  H  H                                          CH.sub.3                                                                            H    Cl  3-OCH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                   CH.sub.3                                                                          H  H  H                                          C.sub.2 H.sub.5                                                                     H    Cl  3-OCH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                   H  H  H  H                                          C.sub.2 H.sub.5                                                                     H    Cl  3-OCH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                   CH.sub.3                                                                          H  H  H                                          n-C.sub.4 H.sub.9                                                                   H    Cl  3-OCH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                   H  H  H  H                                          n-C.sub.4 H.sub.9                                                                   H    Cl  3-OCH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                   CH.sub.3                                                                          H  H  H                                          i-C.sub.3 H.sub.7                                                                   H    Cl  3-OCH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                   H  H  H  H                                          i-C.sub.3 H.sub.7                                                                   H    Cl  3-OCH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                   CH.sub.3                                                                          H  H  H                                          C.sub.5 H.sub.10                                                                         Cl  3-OCH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                   H  H  H  H                                          C.sub.5 H.sub.10                                                                         Cl  3-OCH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                   CH.sub.3                                                                          H  H  H                                          CH.sub.3                                                                            CH.sub.3                                                                            Cl  3-CH.sub.3                                                                           4-CH.sub.3 SO.sub.2                                                                   H  H  H  H                                          CH.sub.3                                                                            CH.sub.3                                                                            Cl  3-CH.sub.3                                                                           4-CH.sub.3 SO.sub.2                                                                   CH.sub.3                                                                          H  H  H                                          CH.sub.3                                                                            n-C.sub.3 H.sub.7                                                                   Cl  3-CH.sub.3                                                                           4-CH.sub.3 SO.sub.2                                                                   H  H  H  H                                          CH.sub.3                                                                            n-C.sub.3 H.sub.7                                                                   Cl  3-CH.sub.3                                                                           4-CH.sub.3 SO.sub.2                                                                   CH.sub.3                                                                          H  H  H                                          CH.sub.3                                                                            n-C.sub.4 H.sub.9                                                                   Cl  3-CH.sub.3                                                                           4-CH.sub.3 SO.sub.2                                                                   H  H  H  H                                          CH.sub.3                                                                            n-C.sub.4 H.sub.9                                                                   Cl  3-CH.sub.3                                                                           4-CH.sub.3 SO.sub.2                                                                   CH.sub.3                                                                          H  H  H                                          CH.sub.3                                                                            H    Cl  3-CH.sub.3                                                                           4-CH.sub.3 SO.sub.2                                                                   H  H  H  H                                          CH.sub.3                                                                            H    Cl  3-CH.sub.3                                                                           4-CH.sub.3 SO.sub.2                                                                   CH.sub.3                                                                          H  H  H                                          C.sub.2 H.sub.5                                                                     H    Cl  3-CH.sub.3                                                                           4-CH.sub.3 SO.sub.2                                                                   H  H  H  H                                          C.sub.2 H.sub.5                                                                     H    Cl  3-CH.sub.3                                                                           4-CH.sub.3 SO.sub.2                                                                   CH.sub.3                                                                          H  H  H                                          n-C.sub.4 H.sub.9                                                                   H    Cl  3-CH.sub.3                                                                           4-CH.sub.3 SO.sub.2                                                                   H  H  H  H                                          n-C.sub.4 H.sub.9                                                                   H    Cl  3-CH.sub.3                                                                           4-CH.sub.3 SO.sub.2                                                                   CH.sub.3                                                                          H  H  H                                          i-C.sub.3 H.sub.7                                                                   H    Cl  3-CH.sub.3                                                                           4-CH.sub.3 SO.sub.2                                                                   H  H  H  H                                          i-C.sub.3 H.sub.7                                                                   H    Cl  3-CH.sub.3                                                                           4-CH.sub.3 SO.sub.2                                                                   CH.sub.3                                                                          H  H  H                                          C.sub.5 H.sub.10                                                                         Cl  3-CH.sub.3                                                                           4-CH.sub.3 SO.sub.2                                                                      H  H  H                                          C.sub.5 H.sub.10                                                                         Cl  3-CH.sub.3                                                                           4-CH.sub.3 SO.sub.2                                                                   CH.sub.3                                                                          H  H  H                                          CH.sub.3                                                                            CH.sub.3                                                                            Cl  3-CH.sub.3                                                                           4-Cl   CH.sub.3                                                                          H  H  H                                          CH.sub.3                                                                            n-C.sub.3 H.sub.7                                                                   Cl  3-CH.sub.3                                                                           4-Cl   H  H  H  H                                          CH.sub.3                                                                            n-C.sub.3 H.sub.7                                                                   Cl  3-CH.sub.3                                                                           4-Cl   CH.sub.3                                                                          H  H  H                                          CH.sub.3                                                                            n-C.sub.4 H.sub.9                                                                   Cl  3-CH.sub.3                                                                           4-Cl   H  H  H  H                                          CH.sub.3                                                                            n-C.sub.4 H.sub.9                                                                   Cl  3-CH.sub.3                                                                           4-Cl   CH.sub.3                                                                          H  H  H                                          CH.sub.3                                                                            H    Cl  3-CH.sub.3                                                                           4-Cl   H  H  H  H                                          CH.sub.3                                                                            H    Cl  3-CH.sub.3                                                                           4-Cl   CH.sub.3                                                                          H  H  H                                          C.sub.2 H.sub.5                                                                     H    Cl  3-CH.sub.3                                                                           4-Cl   H  H  H  H                                          C.sub.2 H.sub.5                                                                     H    Cl  3-CH.sub.3                                                                           4-Cl   CH.sub.3                                                                          H  H  H                                          n-C.sub.4 H.sub.9                                                                   H    Cl  3-CH.sub.3                                                                           4-Cl   H  H  H  H                                          n-C.sub.4 H.sub.9                                                                   H    Cl  3-CH.sub.3                                                                           4-Cl   CH.sub.3                                                                          H  H  H                                          i-C.sub.3 H.sub.7                                                                   H    Cl  3-CH.sub.3                                                                           4-Cl   H  H  H  H                                          i-C.sub.3 H.sub.7                                                                   H    Cl  3-CH.sub.3                                                                           4-Cl   CH.sub.3                                                                          H  H  H                                          C.sub.5 H.sub.10                                                                         Cl  3-CH.sub.3                                                                           4-Cl   H  H  H  H                                          C.sub.5 H.sub.10                                                                         Cl  3-CH.sub.3                                                                           4-Cl   CH.sub.3                                                                          H  H  H                                          CH.sub.3                                                                            CH.sub.3                                                                            Cl  3-OCH.sub.3                                                                          4-Cl   CH.sub.3                                                                          H  H  H                                          CH.sub.3                                                                            n-C.sub.3 H.sub.7                                                                   Cl  3-OCH.sub.3                                                                          4-Cl   H  H  H  H                                          CH.sub.3                                                                            n-C.sub.3 H.sub.7                                                                   Cl  3-OCH.sub.3                                                                          4-Cl   CH.sub.3                                                                          H  H  H                                          CH.sub.3                                                                            n-C.sub.4 H.sub.9                                                                   Cl  3-OCH.sub.3                                                                          4-Cl   H  H  H  H                                          CH.sub.3                                                                            n-C.sub.4 H.sub.9                                                                   Cl  3-OCH.sub.3                                                                          4-Cl   CH.sub.3                                                                          H  H  H                                          CH.sub.3                                                                            H    Cl  3-OCH.sub.3                                                                          4-Cl   H  H  H  H                                          CH.sub.3                                                                            H    Cl  3-OCH.sub.3                                                                          4-Cl   CH.sub.3                                                                          H  H  H                                          C.sub.2 H.sub.5                                                                     H    Cl  3-OCH.sub.3                                                                          4-Cl   H  H  H  H                                          C.sub.2 H.sub.5                                                                     H    Cl  3-OCH.sub.3                                                                          4-Cl   CH.sub.3                                                                          H  H  H                                          n-C.sub.4 H.sub.9                                                                   H    Cl  3-OCH.sub.3                                                                          4-Cl   H  H  H  H                                          n-C.sub.4 H.sub.9                                                                   H    Cl  3-OCH.sub.3                                                                          4-Cl   CH.sub.3                                                                          H  H  H                                          i-C.sub.3 H.sub.7                                                                   H    Cl  3-OCH.sub.3                                                                          4-Cl   H  H  H  H                                          i-C.sub.3 H.sub.7                                                                   H    Cl  3-OCH.sub.3                                                                          4-Cl   CH.sub.3                                                                          H  H  H                                          C.sub.5 H.sub.10                                                                         Cl  3-OCH.sub.3                                                                          4-Cl   H  H  H  H                                          C.sub.5 H.sub.10                                                                         Cl  3-OCH.sub.3                                                                          4-Cl   CH.sub.3                                                                          H  H  H                                           CH.sub.3                                                                           CH.sub.3                                                                            Cl  3-n-C.sub.3 H.sub.7 O                                                                4-Br   H  H  H  H                                          CH.sub.3                                                                            CH.sub.3                                                                            Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                            CH.sub.3                                                                          H  H  H                                          CH.sub.3                                                                            CH.sub.3                                                                            Cl  H     4-NO.sub.2                                                                            H  H  H  H                                          CH.sub.3                                                                            CH.sub.3                                                                            Cl  3-C.sub.2 H.sub.5 O                                                                  4-CH.sub.3 S                                                                          H  H  H  H                                          CH.sub.3                                                                            CH.sub.3                                                                            Cl  H     4-CN   H  H  H  H                                          CH.sub.3                                                                            CH.sub.3                                                                            Cl  3-(CH.sub.3).sub.2 N                                                                 4-Cl   H  H  H  H                                          __________________________________________________________________________

                                      TABLE I-C                                    __________________________________________________________________________      ##STR89##                                                                     Comp.                                                                          No.  R.sup.21                                                                          R.sup.22                                                                          R.sup.23                                                                          R.sup.24                                                                           R.sup.25                                                                           R.sup.26                                                                          R.sup.27                                                                          R.sup.28                                                                          n.sub.D.sup.30 or m.p.                          __________________________________________________________________________     1C.sup.a                                                                            CH.sub.3                                                                          CH.sub.3                                                                          H  H   H   H  H  H  oil                                             2C   H  H  H  H   H   H  H  CN 124-140° C.                              __________________________________________________________________________      .sup.a Prepared in Example IC.                                           

                                      TABLE I-D                                    __________________________________________________________________________      ##STR90##                                                                     Comp.                                                                          No. R.sup.31                                                                          R.sup.32                                                                           R.sup.33                                                                           R.sup.34                                                                          R.sup.35                                                                          R.sup.36                                                                          R.sup.37                                                                            R.sup.38 n.sub.D.sup.30 or                        __________________________________________________________________________                                           m.p.                                     1D  CH.sub.3                                                                          H   H   H  H  H  H    H        viscous oil                              2D  CH.sub.3                                                                          CH.sub.3                                                                           H   H  CH.sub.3                                                                          H  H    H        viscous oil                              3D.sup.a                                                                           H  H   H   H  H  H  H    H        132-135                                  4D  CH.sub.3                                                                          CH.sub.3                                                                           H   H  H  H  H    H        viscous oil                              5D.sup.b                                                                           H  H   CH.sub.3                                                                           CH.sub.3                                                                          H  H  H    H        130-133                                  6D  CH.sub.3                                                                          H   H   H  CH.sub.3                                                                          H  H    H        viscous oil                              7D  CH.sub.3                                                                          CH.sub.3                                                                           H   H  H  H  H    CF.sub.3 52-61                                    8D  H  H   H   H  H  H  H    CF.sub.3 88-94                                    9D  H  H   CH.sub.3                                                                           CH.sub.3                                                                          H  H  H    CF.sub.3 89-97                                    10D CH.sub.3                                                                          CH.sub.3                                                                           H   H  H  H  3-CH.sub.3                                                                          H        119-122                                  11D CH.sub.3                                                                          CH.sub.3                                                                           H   H  H  H  3-Cl H        72-79                                    12D CH.sub.3                                                                          CH.sub.3                                                                           H   H  H  H  H    Cl       118-121                                  13D CH.sub.3                                                                          CH.sub.3                                                                           H   H  H  H  4-Cl H        118-120                                  14D CH.sub.3                                                                          CH.sub.3                                                                           H   H  H  H  5-F  H        130-133                                  15D CH.sub.3                                                                          CH.sub.3                                                                           H   H  H  H  3-CH.sub.3 O                                                                        H        139-142                                  16D CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3                                                                           H  H  H  H    CF.sub.3 viscous oil                              17D CH.sub.3                                                                          CH.sub.3                                                                           H   H  H  H  H    NO.sub.2 viscous oil                              18D CH.sub.3                                                                          CH.sub.3                                                                           H   H  H  H  H    Br       viscous oil                              19D CH.sub.3                                                                          CH.sub.3                                                                           H   H  H  CH.sub.3                                                                          5-CH.sub.3                                                                          H        viscous oil                              20D CH.sub.3                                                                          CH.sub.3                                                                           H   H  H  H  5-CH.sub.3                                                                          H        viscous oil                              21D H  H   H   H  H  H  H    F        123-128                                  22D CH.sub.3                                                                          CH.sub.3                                                                           H   H  H  H  H    F        viscous oil                              23D H  H   H   H  H  H  H    Cl       viscous oil                              24D CH.sub.3                                                                          CH.sub.3                                                                           H   H  H  H  H    SO.sub.2 CH.sub.3                                                                       130-133                                  25D CH.sub.3                                                                          CH.sub.3                                                                           H   H  H  H  H    SO.sub.2 -n-C.sub.3 H.sub.7                                                             viscous oil                              26D H  H   H   H  H  H  H    SO.sub.2 CH.sub.3                                                                       157-159                                  27D H  H   H   H  H  H  H    SO.sub.2 -n-C.sub.3 H.sub.7                                                             120-123                                  28D CH.sub.3                                                                          CH.sub.3                                                                           H   H  H  H  5-F  H        165-195                                  29D CH.sub.3                                                                          CH.sub.3                                                                           H   H  H  H  H    SO.sub.2C.sub.2 H.sub.5                                                                 oil                                      30D CH.sub.3                                                                          CH.sub.3                                                                           H   H  CH.sub.3                                                                          H  H    SO.sub.2CH.sub.3                                                                        gum                                      31D CH.sub.3                                                                          n-C.sub.4 H.sub.9                                                                  H   H  H  H  H    H        viscous oil                              32D H  H   i-C.sub.4 H.sub.9                                                                  H  H  H  H    H        viscous oil                              33D H  H   H   H  H  H  H    SO.sub.2C.sub.2 H.sub.5                                                                 viscous oil                              34D H  H   H   H  H  H  H    CN       viscous oil                              35D H  H   H   H  H  H  H    SO.sub.2 N(CH.sub.3).sub.2                                                              158-159                                  36D CH.sub.3                                                                          CH.sub.3                                                                           H   H  H  H  H    SO.sub.2 N(CH.sub.3).sub.2                                                              120-130                                  37D H  H   H   H  H  H  H    SO.sub.2 N(C.sub.2 H.sub.5).sub.2                                                       158-163                                  38D CH.sub.3                                                                          CH.sub.3                                                                           H   H  H  H  H    SO.sub.2 N(C.sub.2 H.sub.5).sub.2                                                       oil                                      39D CH.sub.3                                                                          CH.sub.3                                                                           H   H  H  H  H                                                                                    ##STR91##                                                                              oil                                      40D H  H   CH.sub.3                                                                           CH.sub.3                                                                          H  H  H    SO.sub.2N(C.sub.2 H.sub.5).sub.2                                                        oil                                      41D H  H   H   H  H  H  H    SC.sub.2 H.sub.5                                                                        oil                                      42D H  H   H   H  H  H  H    S(O)-n-C.sub.3 H.sub.7                                                                  oil                                      43D H  H   H   H  H  H  H    S-n-C.sub.3 H.sub.7                                                                     oil                                      44D CH.sub.3                                                                          CH.sub.3                                                                           H   H  CH.sub.3                                                                          H  H    S-n-C.sub.3 H.sub.7                                                                     oil                                      45D CH.sub.3                                                                          CH.sub.3                                                                           H   H  H  H  H    S-n-C.sub.3 H.sub.7                                                                     oil                                      46D CH.sub.3                                                                          CH.sub.3                                                                           H   H  CH.sub.3                                                                          H  H    SC.sub.2 H.sub.5                                                                        oil                                      47D CH.sub.3                                                                          CH.sub. 3                                                                          H   H  H  H  H    SC.sub.2 H.sub.5                                                                        oil                                      47D CH.sub.3                                                                          CH.sub.3                                                                           H   H  H  H  H    SC.sub.2 H.sub.5                                                                        oil                                      48D H  H   H   H  H  H  H    SCH.sub.3                                                                               94-97                                    49D CH.sub.3                                                                          CH.sub.3                                                                           H   H  CH.sub.3                                                                          H  H    CF.sub.3 oil                                      50D CH.sub.3                                                                          CH.sub.3                                                                           H   H  H  H  H    SCH.sub.3                                                                               oil                                      51D c  H   i-C.sub.3 H.sub.7                                                                  H  H  H  H    H        145-148                                  52D CH.sub.3                                                                          CH.sub.3                                                                           H   H  H  H  5-CH.sub.3 O                                                                        Br       oil                                      53D H  H   CH.sub.3                                                                           CH.sub.3                                                                          H  H  H    Cl       oil                                      54D H  H   H   H  H  H  3-CH.sub.3 O                                                                        Cl       oil                                      55D CH.sub.3                                                                          CH.sub.3                                                                           H   H  H  H  3-CH.sub.3 O                                                                        Cl       oil                                      56D CH.sub.3                                                                          CH.sub.3                                                                           H   H  CH.sub.3                                                                          H  H    CH.sub.3 S                                                                              oil                                      57D H  H   H   H  H  H  H                                                                                    ##STR92##                                                                              120-125                                  58D H  H   CH.sub.3                                                                           CH.sub.3                                                                          H  H  H    CN       175-177                                  59D CH.sub.3                                                                          CH.sub.3                                                                           H   H  H  H  H    CN       151-153                                  60D CH.sub.3                                                                          CH.sub.3                                                                           H   H  CH.sub.3                                                                          H  H    CN       oil                                      61D c  H   H   H  H  H  H    H        oil                                      62D d  H   H   H  H  H  H    H        oil                                      63D H  H   CH.sub.3                                                                           H  H  H  H    Cl       110-115                                  64D H  H   CH.sub.3                                                                           H  H  H  H    SO.sub.2 -n-C.sub.3 H.sub.7                                                             oil                                      65D d  CH.sub.3                                                                           H   H  H  H  H    Cl       oil                                      66D H  H   H   H  H  H  H    SO.sub.2 CHCl.sub.2                                                                     oil                                      67D CH.sub.3                                                                          CH.sub.3                                                                           H   H  H  H  H    SO.sub.2 CHCl.sub.2                                                                     oil                                      68D H  H   H   H  H  H  c    Br       oil                                      69D H  H   H   H  H  H  H    SO.sub.2 CH.sub.2 Cl                                                                    oil                                      70D CH.sub.3                                                                          CH.sub.3                                                                           H   H  H  H  H    SO.sub.2 CH.sub.2 Cl                                                                    wax                                      71D d  CH.sub.3                                                                           H   H  H  H  H    H        oil                                      72D H  H   H   H  H  H  C.sub.2 H.sub.5 O                                                                   Cl       oil                                      73D CH.sub.3                                                                          CH.sub.3                                                                           H   H  CH.sub.3                                                                          H  CH.sub.3 O                                                                          CF.sub.3 oil                                      __________________________________________________________________________      .sup.a Prepared in Example 1D,D'.                                              .sup.b Prepared in Example 2D,D'.                                              .sup. c = C.sub.2 H.sub.5 OC(O)-                                               .sup.d = iC.sub.3 H.sub.7 OC(O)-                                         

                                      TABLE I-E                                    __________________________________________________________________________      ##STR93##                                                                     Comp.                                                                          No. n R.sup.40                                                                          R.sup.41                                                                          R.sup.42                                                                          R.sup.43                                                                          R.sup.44                                                                          R.sup.45                                                                          R.sup.46                                                                          R.sup.47                                                                           R.sup.48                                                                              m.p.                                     __________________________________________________________________________     1E  0 CH.sub.3                                                                          H  H  H  H  H  H  H   H      79-81° C.                         2E  0 CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H  H  H  H  H   H      oil                                      3E.sup.a                                                                           0 CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H  H  CH.sub.3                                                                          H  H   H      oil                                      4E.sup.b                                                                           2 CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H  H  CH.sub.3                                                                          H  H   H      oil                                      5E  0 C.sub.2 H.sub.5                                                                   CH.sub.3                                                                          CH.sub. 3                                                                         H  H  H  H  H   H      oil                                      6E  2 C.sub.2 H.sub.5                                                                   CH.sub.3                                                                          CH.sub.3                                                                          H  H  H  H  H   H      oil                                      7E  0 CH.sub.3                                                                          H  H  H  H  H  H  3-Cl                                                                               Cl     59-64° C.                         8E  2 CH.sub.3                                                                          H  H  H  H  H  H  3-Cl                                                                               Cl     116-119° C.                       9E  0 CH.sub.3                                                                          H  H  H  H  H  H  H   CF.sub.3                                                                              102-106° C.                       10E 2 CH.sub.3                                                                          H  H  H  H  H  H  H   CF.sub.3                                                                              oil                                      11E 0 CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H  H  H  H  H   CF.sub.3                                                                              49-53° C.                         12E 2 CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H  H  H  H  H   CF.sub.3                                                                              oil                                      13E.sup.c                                                                          1 CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H  H  H  H  H   CF.sub.3                                                                              oil                                      14E 0 CH.sub.3                                                                          H  H  H  H  H  H  3-Cl                                                                               SCH.sub.3                                                                             105-107° C.                       15E 1 CH.sub.3                                                                          H  H  H  H  H  H  3-Cl                                                                               S(O)CH.sub.3                                                                          oil                                      16E 0 CH.sub.3                                                                          H  H  H  H  H  H  H   SO.sub.2 n-C.sub.3 H.sub.7                                                            oil                                      17E 0 CH.sub.3                                                                          H  H  H  H  H  H  H   SCH.sub.3                                                                             101-103° C.                       18E 2 CH.sub.3                                                                          H  H  H  H  H  H  H   SO.sub.2 n-C.sub.3 H.sub.7                                                            oil                                      19E 2 CH.sub.3                                                                          H  H  H  H  H  H  H   SO.sub.2 CH.sub.3                                                                     194-196° C.                       20E 0 CH.sub.3                                                                          H  H  H  H  H  H  3-CH.sub.3                                                                         H      40-42° C.                         21E 2 CH.sub.3                                                                          H  H  H  H  H  H  3-CH.sub.3                                                                         H      80-86° C.                         __________________________________________________________________________      .sup.a Prepared in Example 1E,E'.                                              .sup.b Prepared in Example 2E,E'.                                              .sup.c Prepared in Example 3E,e'.                                        

                                      TABLE I-F                                    __________________________________________________________________________      ##STR94##                                                                     Comp.                                 n.sub.D.sup.30                           No. R.sup.50                                                                          R.sup.51                                                                          R.sup.52                                                                          R.sup.53                                                                           R.sup.54                                                                          R.sup.55                                                                          R.sup.56                                                                          R.sup.57                                                                           R.sup.58                                                                               or m.p.                                  __________________________________________________________________________     1F  CH.sub.3                                                                          H  H  H   H  H  H  H   H       35-42° C.                         2F  CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H   H  H  H  H   H       47-53° C.                         3F  CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H   H  H  H  H   Br      oil                                      4F  CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H   H  H  H  H   CN      oil                                      5F  CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H   H  H  H  3-NO.sub.2                                                                         H       oil                                      6F  CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H   H  H  H  5-Cl                                                                               H       oil                                      7F  CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H   H  H  H  H   CH.sub.3 SO.sub.2                                                                      oil                                      8F  CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H   H  CH.sub.3                                                                          H  H   CH.sub.3 SO.sub.3                                                                      oil                                      9F  CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H   H  H  H  3-Cl                                                                               H       oil                                      10F CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H   H  CH.sub.3                                                                          H  H   C.sub.2 H.sub.5 SO.sub.2                                                               oil                                      11F CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H   H  H  H  H   C.sub.2 H.sub.5 SO.sub.2                                                               oil                                      12F CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H   H  H  H  H   n-C.sub.3 H.sub.7 SO.sub.2                                                             oil                                      13F CH.sub.3                                                                          H  H  H   H  H  H  H   CH.sub.3 SO.sub.2                                                                      oil                                      14F CH.sub.3                                                                          H  H  H   H  H  H  H   n-C.sub.3 H.sub.7 SO.sub.2                                                             oil                                      15F CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H   H  H  H  H   CH.sub.3 S                                                                             oil                                      16F C.sub.2 H.sub.5                                                                   CH.sub.3                                                                          CH.sub.3                                                                          H   H  H  H  H   Br      oil                                      17F CH.sub.3                                                                          H  H  H   H  H  H  H   CN      oil                                      18F CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H   H  H  H  H   F       oil                                      19F CH.sub.3                                                                          H  H  H   H  H  H  H   C.sub.2 H.sub.5SO.sub.2                                                                oil                                      20F CH.sub.3                                                                          H  H  H   H  H  H  3-Cl                                                                               H       65-67° C.                         21F CH.sub.3                                                                          H  H  H   H  H  H  3-I H       oil                                      22F CH.sub.3                                                                          H  H  H   H  H  H  3-NO.sub.2                                                                         H       oil                                      23F CH.sub.3                                                                          H  H  H   H  H  H  3-CN                                                                               H       96-101° C.                        24F CF.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H   H  H  H  H   H       oil                                      25F CF.sub.3                                                                          H  H  H   H  H  H  H   H       oil                                      26F CF.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H   H  H  H  H   Br      oil                                      27F CF.sub.3                                                                          H  H  H   H  H  H  H   Cl      82-88° C.                         28F CF.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H   H  H  H  H   Cl      oil                                      29F CF.sub.3                                                                          H  H  H   H  H  H  H   C.sub.2 H.sub.5 S                                                                      oil                                      30F CF.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H   H  H  H  H   C.sub.2 H.sub.5 SO.sub.2                                                               oil                                      31F CF.sub. 3                                                                         H  H  H   H  H  H  H   CN      oil                                      32F CF.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H   H  H  H  H   CN      oil                                      33F.sup.a                                                                          CF.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H   H  CH.sub.3                                                                          H  H   Br      oil                                      34F CH.sub.3                                                                          H  H  H   H  H  H  H   CH.sub.3                                         35F CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H   H  H  H  3-Cl                                                                               C.sub.2 H.sub.5 SO.sub.2                                                               115-117° C.                       36F CH.sub.3                                                                          H  H  H   H  H  H  3-Cl                                                                               C.sub.2 H.sub.5 SO.sub.2                                                               oil                                      37F CH.sub.3                                                                          b  b  H   H  H  H  3-CF.sub.3                                                                         H       oil                                      38F CH.sub.3                                                                          c  H  i-C.sub.3 H.sub.7                                                                  H  H  H  3-NO.sub.2                                                                         H       88-108° C.                        39F CF.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H   H  CH.sub.3                                                                          H  H   CH.sub.3 S                                                                             oil                                      40F CF.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H   H  H  H  H   CH.sub.3 S                                                                             oil                                      41F CF.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H   H  CH.sub.3                                                                          H  H   CH.sub.3 SO.sub.2                                                                      oil                                      42F CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H   H  H  H  H   CF.sub.3                                                                               oil                                      43F CH.sub.3                                                                          H  H  H   H  H  H  H   CF.sub.3                                                                               114-120° C.                       44F CH.sub.3                                                                          H  H  H   H  H  H  3-Cl                                                                               Cl      oil                                      45F CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H   H  H  H  3-Cl                                                                               Cl      oil                                      46F CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H   H  H  H  3-CF.sub.3                                                                         H       oil                                      47F CF.sub.3                                                                          H  H  H   H  H  H  H   CH.sub.3 S                                                                             oil                                      48F CF.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H   H  CH.sub.3                                                                          H  H   CF.sub.3                                                                               oil                                      49F CF.sub.3                                                                          H  H  H   H  H  H  H   CF.sub.3                                                                               oil                                      50F CF.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H   H  H  H  H   CF.sub.3                                                                               oil                                      51F CH.sub.3                                                                          H  H  CH.sub.3                                                                           H  H  H  H   CH.sub.3 SO.sub.2                                                                      oil                                      52F CF.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H   H  CH.sub.3                                                                          H  H   C.sub.2 H.sub.5 SO.sub.2                                                               oil                                      53F CH.sub.3                                                                          H  H  H   H  H  H  H   Br      94-98° C.                         54F CH.sub.3                                                                          H  H  H   H  H  H  d   H       oil                                      __________________________________________________________________________      .sup.a Prepared in Example 1F,F'.                                              .sup.b (CH.sub.2).sub.5                                                        .sup.c C.sub.2 H.sub.5 OC(O)-                                                  .sup.d 3-N(CH.sub.3)COCH.sub.3                                           

                                      TABLE I-G                                    __________________________________________________________________________      ##STR95##                                                                     Comp.                                                                          No. R.sup.60                                                                            R.sup.61                                                                          R.sup.62                                                                          R.sup.63                                                                          R.sup.64                                                                          R.sup.65                                                                            R.sup.66                                                                               m.p. °C.                              __________________________________________________________________________     1G  NO.sub.2                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    H       112-117                                      2G.sup.(a)                                                                         NO.sub.2                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-Cl    76-82                                        3G  Cl   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-SO.sub.2 CH.sub.3                                                                     176-179°                             4G  CH.sub.3                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-SO.sub.2 C.sub.2 H.sub.5                                                             gum                                          5G  CF.sub.3                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-CF.sub.3                                                                             viscous oil                                  6G  NO.sub.2                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-SO.sub.2 CH.sub.2 Cl                                                                 oil                                          7G  Cl   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-F     gum                                          8G  Cl   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          3-OC.sub.2 H.sub.5                                                                  4-SO.sub.2 C.sub.2 H.sub.5                                                             gum                                          9G  NO.sub.2                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-SO.sub.2 CH.sub.3                                                                    gum                                          10G Cl   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-SCH.sub.3                                                                            gum                                          11G CH.sub.3                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          3-NO.sub.2                                                                          H       gum                                          12G I    CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    H       gum                                          13G OCH.sub.3                                                                           CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-Cl    gum                                          14G Cl   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          3-OCH.sub.3                                                                         4-Br    gum                                          15G NO.sub.2                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-SO.sub.2 nC.sub.3 H.sub.7                                                            gum                                          16G NO.sub.2                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-SO.sub.2 N(CH.sub.3).sub.2                                                           gum                                          17G NO.sub.2                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-CN    .sup. 148-150°                        18G SO.sub.2 CH.sub.3                                                                   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    H       gum                                          19G NO.sub.2                                                                            CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-CF.sub.3                                                                             gum                                          20G H    CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-Cl    gum                                          21G H    CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-SCF.sub.3                                                                            gum                                          22G H    CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-OCF.sub.3                                                                            gum                                          23G Cl   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          3-Cl 4-SO.sub.2 C.sub.2 H.sub.5                                                             gum                                          24G H    CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-C(O)CH.sub.3                                                                         gum                                          25G H    CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-SO.sub.2CH.sub.3                                                                     129-131                                      26G H    CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-SCH.sub.3                                                                            89-92                                        27G H    CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-CF.sub.3                                                                             115-125                                      28G H    CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H    4-CN    87-95                                        __________________________________________________________________________      .sup.(a) prepared in Example 1G,G'.                                      

Herbicidal Screening Tests

As previously mentioned, the herein described compounds produced in the above-described manner are phytotoxic compounds which are useful and valuable in controlling various plant species. Selected compounds of this invention were tested as herbicides in the following manner.

Pre-emergence herbicide test.

On the day preceding treatment, seeds of eight different weed species are planted in loamy sand soil in individual rows using one species per row across the width of a flat. The seeds used are green foxtail (FT) (Setaria viridis), watergrass (WG) (Echinochloa crusgalli), wild oat (WO) (Avena fatua), annual morningglory (AMG) (Ipomoea lacunosa), velvetleaf (VL) (Abutilon theophrasti), Indian mustard (MD) (Brassica juncea), redroot pigweed (PW) (Amaranthus refroflexus) or curly dock (CD) (Rumex crispus), and yellow nutsedge (YNG) (Cyperus esculentus). Ample seeds are planted to give about 20 to 40 seedlings per row, after emergence, depending upon the size of the plants.

Using an analytical balance, 600 milligrams (mg) of the compound to be tested are weighed out on a piece of glassine weighing paper. The paper and compound are placed in a 60 milliliter (ml) wide-mouth clear bottle and dissolved in 45 ml of acetone or substituted solvent. Eighteen ml of this solution are transferred to a 60 ml wide-mouth clear bottle and diluted with 22 ml of a water and acetone mixture (19:1) containing enough polyoxyethylene sorbitan monolaurate emulsifier to give a final solution of 0.5% (v/v). The solution is then sprayed on a seeded flat on a linear spray table calibrated to deliver 80 gallons per acre (748 L/ha). The application rate is 4 lb/acre (4.48 Kg/ha).

After treatment, the flats are placed in the greenhouse at a temperature of 70° to 80° F. and watered by sprinkling. Two weeks after treatment, the degree of injury or control is determined by comparison with untreated check plants of the same age. The injury rating from 0 to 100% is recorded for each species as percent control with 0% representing no injury and 100% representing complete control.

The results of the tests are shown in the following Tables

                                      TABLE II-A                                   __________________________________________________________________________     Pre-Emergence Herbicidal Activity                                              Application Rate -- 4.48 kg/ha                                                 Cmpd.                                                                          No. FT  WG WO  AMG VL  MD PW  CD YNS                                           __________________________________________________________________________      1A 100 90 20  40  65  50 35     80                                             2A 80  90 0   30  80  90 20     90                                             3A 0   0  0   40  40  40 0      0                                              4A 100 100                                                                               50  35  100 100                                                                               90     95                                             5A 100 95 65  35  90  85 50     95                                             6A 50  25 0   25  100 100                                                                               35     80                                             7A 80  90 10  60  100 100                                                                               100    80                                             8A 95  95 45  40  100 80 95     95                                             9A 95  100                                                                               55  30  100 90 100    95                                            10A 100 100                                                                               60  20  85  100                                                                               100    95                                            11A 85  100                                                                               30  40  100 100                                                                               100    95                                            12A 85  85 90  75  80  95 90     90                                            13A 85  75 10  10  85  65 95     90                                            14A 40  10 80  0   65  40 65     100                                           15A 40  60 20  30  100 30 75     95                                            16A 80  80 20  55  75  90 40     95                                            17A 20  -- 10  25  100 95 85     90                                            18A 65  -- 30  70  100 100                                                                               85     90                                            19A 45  60 0   30  40  0  20     60                                            20A 30  85 20  40  95  85 40     45                                            21A 80  100                                                                               0   80  100 100                                                                               95     95                                            22A 20  10 0   20  75  30 45     10                                            23A 45  95 10  0   100 85 100    95                                            24A --  100                                                                               0   25  70  90 --     100                                           25A --  100                                                                               25  80  100 100                                                                               --     100                                           26A 40  15 0   0   0   10     0  30                                            27A 40  80 10  20  60  50     30 75                                            28A 65  75 0   65  100 95     75 55                                            29A 100 95 55  10  80  75     85 95                                            30A 20  20 20  10  40  40     50 20                                            31A 75  95 20  20  100 95     75 10                                            32A 90  85 20  0   100 85     75 30                                            33A 80  70 0   40  20  40     90 80                                            34A 60  40 0   20  95  100    100                                                                               60                                            35A 0   10 0   0   10  20     20 10                                            36A 0   0  0   20  100 100    100                                                                               0                                             37A 40  0  0   20  100 60     90 --                                            38A 10  40 0   20  90  80     20 20                                            39A 80  10 0   0   0   0      0  90                                            40A 60  0  0   0   0   0      0  90                                            41A 100 100                                                                               85  40  95  100    100                                                                               100                                           42A 60  100                                                                               25  0   0   0      0  25                                            43A 100 100                                                                               45  40  80  90     90 100                                           44A 90  100                                                                               0   60  100 100    100                                                                               95                                            45A 100 100                                                                               0   60  100 100    100                                                                               100                                           46A 20  60 0   100 100 100    100                                                                               20                                            47A 60  70 20  100 100 100    100                                                                               60                                            48A 60  0  0   0   0   0      0  40                                            49A 100 100                                                                               50  10  60  20     90 100                                           50A 100 100                                                                               80  10  60  60     90 100                                           51A 100 100                                                                               90  100 100 100    85 100                                           52A 100 100                                                                               60  10  100 100    60 100                                           53A 0   20 0   0   20  20     0  10                                            54A 10  45 10  0   0   0      0  40                                            55A 90  100                                                                               60  100 100 100    90 100                                           56A 40  70 40  40  40  60     70 50                                            57A 100 100                                                                               90  100 100 100    85 100                                           58A 90  95 0   20  20  40     40 100                                           59A 95  100                                                                               85  75  100 100    90 98                                            60A 95  100                                                                               50  50  100 100    90 98                                            61A 100 100                                                                               75  100 100 100    95 95                                            62A 100 100                                                                               95  75  100 100    100                                                                               80                                            63A 100 100                                                                               40  65  100 100    100                                                                               95                                            64A 100 100                                                                               98  100 100 100    100                                                                               90                                            65A 100 100                                                                               80  100 100 100    100                                                                               90                                            66A 100 100                                                                               75  100 100 100    100                                                                               98                                            73A 100 100                                                                               60  80  100 100    75 90                                            74A 100 100                                                                               70  80  100 100    80 100                                           75A 70  100                                                                               0   50  100 100    100                                                                               80                                            76A 40  90 25  10  100 100    100                                                                               10                                            77A 100 100                                                                               90  100 100 100    85 --                                            78A 100 100                                                                               80  100 100 100    90 --                                            79A 50  100                                                                               50  50  95  100    100                                                                               60                                            80A 0   0  0   0   0   0      0  0                                             81A 100 100                                                                               50  15  100 100    90 100                                           84A 100 100                                                                               85  0   0   100    20 100                                           88A 60  95 35  95  100 100    95 80                                            89A 75  100                                                                               40  100 100 100    95 60                                            90A 100 100                                                                               90  100 100 100    100                                                                               85                                            105A                                                                               80  95 25  0   95  50     70 50                                            117A                                                                               95  100                                                                               0   25  100 100    50 95                                            118A                                                                               100 100                                                                               60  100 100 100    100                                                                               85                                            121A                                                                               95  100                                                                               50  75  100 95     100                                                                               80                                            125A                                                                               100 100                                                                               50  80  100 100    100                                                                               85                                            126A                                                                               70  100                                                                               80  80  100 100    100                                                                               80                                            127A                                                                               100 100                                                                               100 100 100 100    -- 80                                            128A                                                                               100 100                                                                               100 100 100 100    -- 80                                            129A                                                                               100 100                                                                               95  90  100 100    -- 80                                            131A                                                                               70  85 0   20  95  98     95 90                                            132A                                                                               100 100                                                                               95  90  100 100    -- 80                                            133A                                                                               100 100                                                                               100 100 100 100    -- 80                                            135A                                                                               100 100                                                                               100 80  100 100    -- 80                                            __________________________________________________________________________

                  TABLE II-B                                                       ______________________________________                                         Pre-Emergence Herbicidal Activity                                              Application Rate -- 4.48 kg/ha                                                 Cmpd.                                                                          No.    FT     WG     WO   AMG   VL   MD   CD   YNS                             ______________________________________                                          1B    0      85     10   75    100  80   80   75                               2B    90     100    65   100   100  100  100  100                              4B    100    100    80   60    100  80   90   100                              5B    80     100    20   40    100  100  80   100                              6B    40     100    0    40    100  100  80   100                              7B    100    100    100  80    100  100  90   100                              8B    100    100    60   45    60   60   80   100                              9B    60     100    40   20    60   60   60   100                             10B    100    100    40   5     80   60   80   100                             11B    100    100    90   10    20   20   40   100                             12B    0      20     0    0     10   20   10    0                              13B    100    100    90   40    100  100  100  100                             15B    90     90     50   20    --   100  100  80                              16B    100    100    95   100   100  100  90   100                             17B    100    100    100  100   100  100  100  97                              18B    100    100    85   100   100  100  90   95                              19B    100    100    95   100   100  100  100  95                              20B    100    100    85   100   100  100  100  90                              21B    100    100    100  100   100  100  100  95                              22B    100    100    80   100   100  100  100  90                              25B    100    100    75   80    100  100  100  90                              26B    100    100    65   30    100  100  100  90                              27B    20     95     60   5     100  100  90   100                             28B    100    100    80   20    90   40   80   100                             29B    100    100    70   20    100  100  100  100                             30B    100    100    80   60    100  100  80   100                             31B    80     100    40   10    60   60   80   100                             32B    20     40     10   0     --   60   100  60                              33B    0      10     0    0     10   10   0     0                              34B    100    100    90   80    100  100  90   100                             35B    100    100    90   40    90   90   90   90                              36B    100    100    85   0     95   85   95   90                              37B    90     90     50   20    --   100  100  80                              39B    15     100    0    50    100  80   70   40                              40B    0      10     0    0     10   10   0     0                              41B    0      20     0    0     10   20   10    0                              42B    100    100    90   45    100  100  65   100                             43B    100    100    90   100   100  100  100  90                              44B    100    100    85   100   100  100  100  95                              45B    65     100    0    0     100  20   20   90                              46B    100    100    0    20    100  100  98   85                              47B    100    100    90   85    100  100  100  95                              48B    100    100    85   15    100  100  85   95                              49B    100    100    65   0     100  100  50   50                              50B    80     80     55   0     98   55   80   65                              51B    95     95     10   0     65   0    25   60                              52B    100    100    100  100   100  100  100  50                              53B    100    100    75   100   100  100  100  50                              54B    100    100    60   15    100  100  100  80                              55B    100    100    55   15    100  100  90   95                              56B    100    100    60   20    95   100  90   10                              57B    5      10     0    0     40   20   0     0                              58B    10     40     10   10    95   40   100  80                              59B    100    100    75   80    100  100  100  75                              60B    100    100    90   100   100  100  85   --                              61B    100    100    80   100   100  100  100  --                              62B    95     100    50   95    100  100  85   --                              63B    100    100    70   100   90   100  100  --                              64B    100    100    75   100   100  100  85   --                              65B    100    100    55   40    100  100  90   70                              66B    100    100    65   35    100  100  100  95                              67B    100    100    30   15    100  100  95   90                              71B    100    100    80   100   100  100  80   --                              72B    100    100    40   100   100  100  90   75                              73B    90     100    40   100   100  100  95   50                              74B    100    100    85   95    100  100  90   80                              75B    100    100    100  70    100  100  100  95                              77B    100    100    55   40    100  100  90   70                              81B    90     95     60   10    25   75   90    0                              82B    40     90     20   35    100  --   75   20                              91B    100    100    85   100   100  100  80   90                              101B   85     90     0    0     95   50   50   75                              ______________________________________                                    

                  TABLE II-C                                                       ______________________________________                                         Pre-Emergence Herbicidal Activity                                              Application Rate -- 4.48 kg/ha                                                 Cmpd.                                                                          No.    FT     WG     WO   AMG   VL   MD   CD   YNS                             ______________________________________                                         1C     65     80     65   55    90   90   35   0                               ______________________________________                                    

                  TABLE II-D                                                       ______________________________________                                         Pre-Emergence Herbicidal Activity                                              Application Rate -- 4.48 kg/ha                                                 Cmpd.                                                                          No.    FT     WG     WO   AMG   VL   MD   CD   YNS                             ______________________________________                                          1D    100    100    85   30    100  100  90   90                               2D    100    100    100  50    100  100  95   95                               3D    100    100    85   25    100  100  100  95                               4D    100    100    100  20    100  85   95   90                               5D    100    100    45   25    100  100  90   90                               6D    100    100    95   40    100  100  85   90                               9D    100    100    90   90    100  100  80   90                              10D    100    90     20   10    100  70   100  90                              11D    90     100    50   230   100  100  90   90                              12D    100    100    95   80    100  100  90   90                              13D    40     75     0    10    80   100  100  90                              14D    50     0      0    0     100  80   70   90                              15D    65     95     20   15    100  80   90   85                              17D    100    100    60   30    100  100  90   35                              18D    100    100    100  100   100  100  100  95                              19D    100    100    0    50    100  100  100  95                              20D    75     100    0    25    100  90   65   90                              21D    100    100    100  80    100  100  90   95                              22D    100    100    100  80    100  100  95   95                              23D    100    100    98   95    100  100  100  95                              25D    100    100    80   100   100  100  80   --                              26D    100    100    75   100   100  100  80   --                              27D    90     100    50   100   100  100  100  90                              28D    75     50     50   0     100  100  90   65                              30D    100    100    85   100   100  100  95   90                              31D    85     75     0    25    100  25   0    35                              32D    83     85     35   20    95   100  75   50                              36D    100    100    50   100   100  100  100  75                              37D    20     75     0    20    100  95   100  75                              38D    85     95     40   60    100  100  75   85                              39D    85     95     45   75    100  95   70   90                              51D    60     60     35   0     25   0    0    30                              52D    75     75     0    50    90   75   40    0                              65D    100    100    80   100   100  100  --   80                              ______________________________________                                          A blank (--) indicates that the weed was not tested.                     

                  TABLE II-E                                                       ______________________________________                                         Pre-Emergence Herbicidal Activity                                              Application Rate -- 4.48 kg/ha                                                 Cmpd.                                                                          No.    FT     WG     WO   AMG   VL   MD   CD   YNS                             ______________________________________                                         1E     0      0      0    0     0    0    0    20                              2E     25     30     30   0     70   0    40   30                              3E     25     20     0    0     0    0    0     0                              4E     100    100    90   60    100  100  100  90                              5E     50     60     40   50    50   60   90   50                              6E     100    95     50   40    40   60   99   70                              16E    80     100    50   60    100  90   90   90                              20E    100    100    30   15    100  100  90   85                              21E    100    100    --   30    100  95   100  80                              ______________________________________                                          A blank (--) indicates that the weed was not tested.                     

                  TABLE II-F                                                       ______________________________________                                         Pre-Emergence Herbicidal Activity                                              Application Rate -- 4.48 kg/ha                                                 Cmpd.                                                                          No.    FT     WG     WO   AMG   VL   MD   CD   YNS                             ______________________________________                                          1F    40     20     0    0     0    0    0    100                              2F    60     70     0    0     0    0    90   100                              3F    100    100    50   50    100  100  85   90                               4F    100    100    90   30    100  85   95   95                               5F    100    100    80   10    100  100  100  95                               6F    20     35     25   15    90   85   40   85                               7F    100    100    90   100   100  100  100  95                               8F    100    100    90   100   100  100  100  95                               9F    100    100    0    0     100  80   100  90                              10F    100    100    100  100   100  100  100  95                              11F    100    100    70   100   100  100  97   95                              12F    100    100    60   100   100  100  100  95                              13F    100    100    60   100   100  100  100  95                              14F    80     100    50   80    100  100  90   90                              15F    100    100    80   100   100  100  100  --                              16F    50     75     0    25    100  100  95   60                              17F    100    100    40   100   100  100  100  85                              18F    100    100    0    20    100  100  80   70                              20F    70     75     0    25    100  95   100  60                              21F    50     60     0    0     100  80   80   60                              22F    100    95     35   25    100  100  90   50                              23F    95     100    40   20    100  100  90   50                              24F    100    100    90   0     45   85   80   90                              25F    100    100    25   60    100  100  100  75                              34F    35     40     10   0     60   25   0    70                              37F    50     60     0    0     60   0    50    0                              38F    35     40     0    0     0    0    0     0                              52F    85     100    30   95    100  100  --   80                              53F    100    100    0    85    100  100  --   80                              54F    100    100    90   25    100  100  --   80                              ______________________________________                                          A blank (--) indicates that the weed was not tested.                     

                  TABLE II-G                                                       ______________________________________                                         Pre-Emergence Herbicidal Activity                                              Application Rate -- 4.48 kg/ha                                                 Cmpd.                                                                          No.    FT      WG     WO   AMG    VL   MD    YNS                               ______________________________________                                          1G    100     100    90   100    100  100   80                                 2G    100     100    90   100    100  100   80                                 3G    100     100    90   100    100  100   80                                 4G    100     100    90   100    100  100   80                                 5G    100     100    90   100    100  100   80                                 6G*   100     100    100  100    100  --    20                                 7G    100     100    80   100    100  100   80                                 8G     85     100    80   100    100  100   80                                 9G    100     100    80   100    100  100   80                                10G    100     100    80   100    100  100   80                                11G    100     100    80   100    100  100   80                                12G    100     100    80    90    100  100    0                                13G    100     100    70   100    100  100    0                                14G    100     100    75   100    100  100   90                                15G    100     100    80   100    100  100   90                                16G    100     100    90   100    100  100   80                                17G    100     100    80   100    100  100   80                                18G    100     100    90    85    100  100   80                                19G    100     100    100  100    100  100   80                                20G     70      95    10   100    100  100    0                                21G    100     100    100  100    100  100   80                                22G    100     100    90   100    100  100   80                                23G    100     100    100  100    100  100   80                                24G     0       80     0    25     80   70    0                                25G    100     100    80   100    100  100   80                                26G    100     100    100   80    100  100   80                                27G    100     100    100  100    100  100   80                                28G    100     100    90   100    100  100   80                                ______________________________________                                          A blank (--) indicates that the weed was not tested.                           *= Tested at 0.56 kg/ha.                                                 

Post-Emergence Herbicide Test:

This test is conducted in an identical manner to the testing procedure for the pre-emergence herbicide test, except the seeds of the eight different weed species are planted 10-12 days before treatment. Also, watering of the treated flats is confined to the soil surface and not to the foliage of the sprouted plants.

The results of the post-emergence herbicide test are reported in Table III.

                                      TABLE III-A                                  __________________________________________________________________________     Post-Emergence Herbicidal Activity                                             Applicaton Rate - 4.48 kg/ha                                                   Cmpd.                                                                          No. FT  WG WO  AMG VL  MD PW  CD YNS                                           __________________________________________________________________________      1A 60  70 20  40  60  60 35     60                                             2A 30  70  0  50  90  85 30     80                                             3A  0  30  0  70  100 90 55     70                                             4A 95  98 20  98  100 100                                                                               30     95                                             5A 80  80 75  50  60  80  0     95                                             6A 40  40 10  60  100 100                                                                               75     65                                             7A 60  75 40  60  100 75 100    75                                             8A 85  80 75  70  95  80 90     90                                             9A 85  80 75  70  95  80 90     90                                            10A 95  85 90  60  95  95 80     95                                            11A 50  80 35  55  100 100                                                                               95     80                                            12A 45  75 50  55  75  60 50     80                                            13A 30  60 20  60  80  50 60     70                                            14A 20  10 20  50  45  40 40      0                                            15A 65  95  0  65  95  30 100    80                                            16A 65  80 20  85  85  30 30     80                                            17A 75  80 30  70  100 100                                                                               85     90                                            18A 100 95 10  100 100 100                                                                               100    90                                            19A 60  80 40  70  100 75 80     90                                            20A 65  80 10  85  95  95 100    70                                            21A 30  55  0  80  100 80 65     80                                            22A  0  30  0  20  45   0 30     20                                            23A 85  90 40  85  100 95 100    90                                            24A  0  80  0  70  90  74 --     100                                           25A 100 100                                                                               75  90  100 100                                                                               --     100                                           26A 45  30  0  40  70  65      0 45                                            27A 75  80 30  65  50  45     85 85                                            28A 75  60 60  75  100 70     80 25                                            29A 85  85 85  75  85  65     65 85                                            30A 75  50 20  10   0   0     20 40                                            31A 60  60 20  40  40  70     100                                                                               40                                            32A 60  25 20  40  90  65     20 40                                            33A 10   0  0  10  10  10     100                                                                               40                                            34A 10  10  0   5  50  30     80  0                                            35A  0   0  0  10  60  30     40  0                                            36A  0   0  0  20  20  20      0  0                                            37A  0   0  0  30  40  20     80  0                                            38A 10  10 10  20  10  20     20 10                                            39A 40  40 20   0   0   0      5 80                                            40A 90  70 40  20  60  80     20 65                                            41A 60  85 85  20  40  60     100                                                                               100                                           42A 60  50 40  70  20  40     60 60                                            43A 100 80 30  60  100 100    80 100                                           44A 80  85  0  60  90  90     100                                                                               80                                            45A 90  90 10  100 100 100    100                                                                               90                                            46A 80  100                                                                                0  60  100 100    100                                                                               100                                           47A 100 100                                                                                0  60  100 100    100                                                                               100                                           48A 40  40 20  10  10  10     90 40                                            49A 40  40 40  80  100 100    60 60                                            50A 80  60 60  50  50  60     80 70                                            51A 80  80 80  95  100 100    100                                                                               90                                            52A 60  60 20  20  40  40     90 60                                            53A 10  20 20   0   0   0      0 20                                            54A 20  40 20   5   0   0      0 40                                            55A 40  40 40  60  60  60     80 90                                            56A 100 100                                                                               75  80  100 100    100                                                                               90                                            57A 80  80 80  95  100 100    100                                                                               90                                            58A 60  70 10  70  10  10     20 80                                            59A 100 100                                                                               90  100 --  100    100                                                                               50                                            60A 100 100                                                                               100 100 --  100    100                                                                               70                                            61A 90  85 90  85  --  100    100                                                                               80                                            62A 100 85 100 75  100 100    100                                                                               35                                            63A 70  80 20  100 100 100    35 40                                            64A 75  75 90  70  90  70     40 40                                            65A 100 70 100 55  90  95     100                                                                               40                                            66A 100 75 100 90  95  95     100                                                                               20                                            73A 100 100                                                                               95  100 100 100    55 30                                            74A 100 95 75  100 100 100    85 40                                            75A 100 100                                                                               30  95  80  100    80 40                                            76A 80  80 75  75  100 95     95 25                                            77A 80  80 80  90  90  80     90 80                                            78A 80  85 75  85  80  95     100                                                                               50                                            79A 50  65 35  90  100 100    90 --                                            80A 40  40 10  20  60   0      0 30                                            81A 90  70 60  40  60  60     90 70                                            84A 100 100                                                                               100 20  40  40     80 60                                            88A 100 95 90  100 85  100    100                                                                               50                                            89A 100 100                                                                               75  85  75  85     95 50                                            90A 100 85 90  90  85  90     100                                                                               55                                            91A 100 100                                                                               100 100 95  100    95 60                                            105A                                                                               35  50 --  35  100 80     60 30                                            117A                                                                               40  60  0  25  50  50     80 --                                            118A                                                                               95  85 85  100 100 90     80 80                                            121A                                                                               65  85 40  100 100 100    60 50                                            125A                                                                               90  95 75  70  100 90     100                                                                               60                                            126A                                                                               40  50 20  40  60  50     100                                                                               80                                            127A                                                                               100 95 100 95  100 100       80                                            128A                                                                               85  95 80  60  100 95        80                                            129A                                                                               65  90 60  60  100 98        70                                            130A                                                                               100 95 95  95  100 100       70                                            131A                                                                                0  20  0   0  30  75     10  0                                            132A                                                                               95  100                                                                               100 80  95  95        50                                            133A                                                                               80  95 90  60  85  85        60                                            135A                                                                               70  100                                                                               100 75  100 95        70                                            __________________________________________________________________________

                  TABLE III-B                                                      ______________________________________                                         Post-Emergence Herbicidal Activity                                             Application Rate -- 4.48 kg/ha                                                 Cmpd.                                                                          No.    FT     WG     WO   AMG   VL   MD   CD   YNS                             ______________________________________                                          1B    85     95     20   95    100  100  95   95                               2B    90     90     80   100   90   90   --   80                               4B    60     60     90   40    60   60   90   70                               5B    40     60     10   20    40   40   90   80                               6B    40     50     10   60    20   20   60   50                               7B    80     80     80   60    60   90   6    60                               8B    100    80     60   30    80   80   80   80                               9B    70     70     60   40    60   60   80   70                              10B    40     40     60   30    60   60   90   60                              11B    80     90     60   45    90   90   100  80                              12B    25     45     10   20    20   20   60   45                              13B    100    100    95   70    60   60   80   60                              15B    100    60     50   80    90   90   40   60                              16B    60     60     80   80    90   90   60   65                              17B    100    70     90   100   --   90   98   70                              18B    100    85     100  85    --   100  100  65                              19B    100    80     85   100   100  90   100  70                              20B    90     65     90   85    70   60   100  40                              21B    40     40     10   0     0    0    0     0                              22B    40     70     80   90    90   100  95   40                              25B    40     70     40   40    40   60   70   50                              26B    65     70     80   40    90   80   70   80                              27B    100    80     60   20    90   90   80   45                              28B    90     60     60   60    60   60   40   70                              29B    90     70     70   40    70   70   60   60                              30B    100    90     70   50    100  100  80   80                              31B    40     50     20   10    20   20   0    40                              32B    25     40     40   90    100  100  40   40                              33B    20     40     10   60    90   90   60   40                              34B    90     80     80   80    100  100  80   50                              35B    60     50     50   20    60   60   80   60                              36B    100    80     80   75    --   100  100  45                              37B    100    60     50   80    90   90   40   60                              39B    90     80     25   30    30   45   50   30                              40B    20     40     10   60    90   90   60   40                              41B    25     45     10   20    20   20   60   45                              42B    90     80     80   80    100  100  100  70                              43B    80     90     95   97    100  100  100  50                              44B    100    95     95   95    40   100  100  30                              45B    30     65     0    30    45   40   65   50                              46B    70     75     0    65    100  100  50   70                              47B    100    100    100  90    100  100  100  85                              48B    100    65     80   50    100  100  60   60                              49B    60     70     70   40    80   70   30   50                              50B    0      60     40   60    100  90   20   30                              51B    100    75     80   40    100  50   20   30                              52B    90     100    100  100   100  100  100  40                              53B    60     70     70   70    90   65   40   60                              54B    100    100    85   100   100  100  100  60                              55B    95     85     90   100   100  100  90   45                              56B    85     100    0    10    15   95   40   50                              57B    85     70     65   0     0    0    0    35                              58B    20     40     10   15    70   40   35   40                              59B    100    95     100  95    100  95   100  40                              60B    65     75     75   80    90   85   80   60                              61B    80     80     70   95    80   85   80   50                              62B    100    80     25   80    75   80   85   35                              63B    100    100    40   95    95   100  95   50                              64B    75     70     50   90    90   100  90   50                              65B    100    80     80   60    85   60   0    --                              66B    98     90     60   35    --   100  60   90                              67B    70     65     20   15    95   40   70   45                              71B    95     50     50   80    80   80   65   50                              72B    100    85     75   75    65   85   70   60                              73B    100    95     95   85    75   85   95   40                              74B    100    85     95   90    80   95   65   50                              75B    100    80     80   30    50   60   100  40                              81B    50     80     35   70    70   90   80   10                              82B    25     60     50   35    50   90   50   25                              91B    80     60     40   60    75   90   60   75                              101B   10     35     --   30    75   70   40   50                              ______________________________________                                          (--) = Specie did not germinate for some reason.                         

                  TABLE III-C                                                      ______________________________________                                         Post-Emergence Herbicidal Activity                                             Application Rate -- 4.48 kg/ha                                                 Cmpd.                                                                          No.    FT     WG     WO   AMG   VL   MD   CD   YNS                             ______________________________________                                         1C     98     95     70   60    100  55   100  90                              ______________________________________                                    

                  TABLE III-D                                                      ______________________________________                                         Post-Emergence Herbicidal Activity                                             Application Rate - 4.48 kg/ha                                                  Cmpd.                                                                          No.   FT     WG     WO   AMG   VL   MD    CD   YNS                             ______________________________________                                          1D   95     75     85   70    100  90    85   40                               2D   45     70     95   75    100  90    100  65                               3D   100    80     100  90    --   100   100  80                               4D   100    80     100  100   --   100   85   75                               5D   90     70     45   60     95  70    60   80                               6D   95     75     80   70    100  90    90   65                               9D   100    90     90   100   100  100   95   85                              10D   45     75     10   15    100  100   20   75                              11D   100    70     60   75    100  100   100  45                              12D   100    75     100  100   100  100   90   90                              13D   30     55      0   30     60  60    15   60                              14D   20     65      0   40     70  60    40   25                              15D   20     75     30   20    100  70    60   40                              17D   85     80     50   65     95  95    100  60                              18D   100    95     100  100   100  100   100  75                              19D   20     95     30   100   100  35    30   70                              20D   30     80     15   100   100  45    20   70                              21D   100    80     100  55    100  90    100  80                              22D   100    80     100  60    100  95    95   95                              23D   100    90     90   100   100  100   85   70                              25D   70     75     50   85     90  85    60   75                              26D   100    85     85   95     95  95    90   60                              27D   90     90     60   100   100  100   100  --                              28D   15     45     20   50     75  80    15   30                              30D   100    100    80   85     85  85    100  --                              31D   80     90     100  100   100  100   100  60                              32D   75     85     85   75     75  90    95   50                              36D   35     50     35   70      50 50    35   60                              37D   60     75     15   70     70  90    90   40                              38D   95     90     65   70     90  90    100  50                              39D   95     85     30   50     70  80    100  50                              51D   60     75     60   35     30  60    40   60                              52D   60     75     25   100   100  100   100  75                              65D   70     50     70   90     80  85    --   80                              ______________________________________                                          A blank (--) indicates the weed was not tested.                          

                  TABLE III-E                                                      ______________________________________                                         Post-Emergence Herbicidal Activity                                             Application Rate - 4.48 kg/ha                                                  Cmpd.                                                                          No.   FT     WG     WO   AMG   VL   MD    CD   YNG                             ______________________________________                                         1E    20     20     10   20    40   40    20   40                              2E     0     60     60   50    70   30     0   15                              3E    20     20      0   10     0   20     0   20                              4E    85     90     100  45    75   30    80   65                              5E    55     50     60   50    75   85    65   --                              6E    70     70     50   60    80   70    90   --                              16E   95     95     40   100   100  100   100  90                              20E   95     75     35   40    95   75    35   80                              21E   80     70     30   45    80   90    50   70                              ______________________________________                                          A blank (--) indicates the weed was not tested.                          

                  TABLE III-F                                                      ______________________________________                                         Post-Emergence Herbicidal Activity                                             Application Rate - 4.48 kg/ha                                                  Cmpd.                                                                          No.   FT     WG     WO   AMG   VL   MD    CD   YNG                             ______________________________________                                          1F   60     40     20   30    40   40    50   60                               2F   50     40     10   20    20   20    40   60                               3F   100    100    85   100   100  100   100  75                               4F   100    100    95   85    100  95    100  60                               5F   95     95     100  65    90   25    70   45                               6F   40     30      0   20    90   25    20   70                               7F   100    100    100  100   100  100   100  90                               8F   100    95     100  100   100  100   100  70                               9F   65     65      0   20    80   65    90   80                              10F   100    100    100  100   100  100   100  70                              11F   85     90     90   85    90   80    30   60                              12F   100    90     65   80    100  100   100  50                              13F   100    95     100  100   100  100   90   --                              14F   100    100    100  100   100  100   100  50                              15F   25     35     15   30    80   25    20    0                              16F   100    85     70   75    90   90    50   --                              17F   100    100    100  100   100  100   100  --                              18F   90     85     85   85    90   95    70   40                              20F   40     60     10   60    100  100   100  50                              21F   35     60     10   60    100  100   80   60                              22F   95     95     35   100   100  100   90   50                              23F   100    100    40   100   100  100   90   50                              24F   100    75     100  60    --   100   100  60                              25F   95     95     90   95    100  100   95   35                              34F   50     40      0   35    50   70    30   50                              37F   20     60       0  30    30   50    50   50                              38F   25     50      0   25    25   50    20   20                              52F    0     60     50   50    10   50    --   20                              53F    0     50      0   50    50   50    --   30                              54F   90     75     60   50    50   80    --   80                              ______________________________________                                          A blank (--) indicates the weed was not tested.                          

                  TABLE III-G                                                      ______________________________________                                         Post-Emergence Herbicidal Activity                                             Application Rate - 4.48 kg/ha                                                  Cmpd.                                                                          No.   FT     WG      WO    AMG   VL    MD    YNG                               ______________________________________                                          1G   100    95      90    90    100   100   80                                 2G   100    100     100   100   100   100   80                                 3G   100    100     95    100   100   100   90                                 4G   100    100     100   100   100   100   90                                 5G   100    100     100   100   100   100   100                                6G*  10     80      50    75    40    --     0                                 7G   70     75      70    90    90    80    80                                 8G   50     80      70    90    90    80    30                                 9G   70     80      70    90    90    80    30                                10G   75     80      70    80    60    50    70                                11G   70     80      70    80    80    80    80                                12G   100    75      90    75    80    80    80                                13G   60     70      70    100   100   100   80                                14G   20     70      40    60    80    80    70                                15G   90     70      70    75    80    90    70                                16G   50     70      80    60    80    90    70                                17G   90     60      70    65    80    80    80                                18G   30     50      80    95    95    80    70                                19G   100    100     95    90    100   100   80                                20G   10     40       5    70    80    90    70                                21G   95     90      95    95    100   100   70                                22G   80     90      90    80    100   100   70                                23G   90     80      80    80    90    80    30                                24G    0     30       0    40    80    20     0                                25G    0     20       0    10    10    20     0                                26G   80     70      70    80    80    80    70                                27G   90     90      90    80    80    90    60                                28G   70     65      50    80    80    80    70                                ______________________________________                                          A blank (--) indicates the weed was not tested.                                * Tested at 0.56 kg/ha.                                                  

Pre-Emergence Multi-Weed Herbicide Test

Several compounds were evaluated at an application rate of 2 lb/acre (2.24 kg/ha) or 1 lb/acre (1.12 kg/ha) for pre-emergence activity against a larger number of weed species.

The process was generally similar to the pre-emergence herbicide test described above except that only 300 or 150 milligrams of test compound were weighed out and the application rate was 40 gallons per acre.

Redroot pigweed (PW) and curly doct (CD) were eliminated in this test and the following weed species were added:

    ______________________________________                                         Grasses:                                                                       ______________________________________                                         downy brome  Bromus tectorum                                                                              (DB)                                                annual ryegrass                                                                             Lolium multiflorum                                                                           (ARG)                                               rox-orange   Sorghu bicolor                                                                               (SHC)                                               sorghum                                                                        hemp sesbania                                                                               Sesbania exaltata                                                                            (SESB)                                              nightshade   Solanum sp.   (SP)                                                cocklebur    Xattiium sp.  (CB)                                                ______________________________________                                    

The results of the 2.24 kg/ha test are shown in Table IV and the results of the 1.12 kg/ha test are shown in Table VI.

Post-Emergence Multi-Weed Herbicide Test

Several compounds were evalated at an application rate of 2 lb/acre (2.24 kg/ha) or 1 lb/acre (1.12 kg/ha) for post-emergence activity against the larger number of weed species that are used in the pre-emergent multi-herbicide test.

The process was generally similar to the post-emergence herbicide test described above except that only 300 or 150 milligrams of test compound were weighed out and the application rate was 40 gallons per acre.

The results of the 2.24 kg/ha test are shown in Table V and the results for the 1.12 kg/ha test are shown in Table VII.

                                      TABLE IV-A                                   __________________________________________________________________________     Pre-Emergence Multi-weed Herbicide Test                                        Application Rate - 2.24 kg/ha                                                  Cmpd.                                                                          No. DB FT ARG WG SHC                                                                               WO BSG                                                                               AMG SESB                                                                               VL SP                                                                               MD YNS                                                                               CB                                __________________________________________________________________________     67A 20 90 25   98                                                                                80                                                                               60 90 45  90   45                                                                               20                                                                                85                                                                               85 15                                68A 65 98 98  100                                                                               100                                                                               60 95 100 100 100                                                                               80                                                                               100                                                                               95 100                               69A 65 100                                                                               70  100                                                                               100                                                                               65 95 100 95   70                                                                               65                                                                               100                                                                               90 --                                70A 98 100                                                                               100 100                                                                               100                                                                               90 98 90  100  90                                                                               60                                                                               100                                                                               95 80                                71A 60 20 100 100                                                                               100                                                                               80 95 35  40  100                                                                               20                                                                                90                                                                               100                                                                               40                                72A 100                                                                               100                                                                               100 100                                                                               100                                                                               100                                                                               100                                                                               100 90  100                                                                               60                                                                               100                                                                               100                                                                               20                                83A 15 45 25   90                                                                                15                                                                                 5                                                                               90 45  35   20                                                                                0                                                                                20                                                                               75 --                                86A 20  0 15   60                                                                                60                                                                               20 70 25  45  100                                                                               20                                                                               100                                                                               15 35                                87A 100                                                                               90 85  100                                                                                85                                                                               25 30 35  85  100                                                                               85                                                                               100                                                                               95 40                                __________________________________________________________________________

                                      TABLE VI-A                                   __________________________________________________________________________     Post-Emergence Multi-weed Herbicide Test                                       Application Rate - 2.24 hg/ha                                                  Cmpd.                                                                          No. DB FT ARG WG SHC                                                                               WO BSG                                                                               AMG SESB                                                                               VL SP MD YNS                                                                               CB                               __________________________________________________________________________     86A 60 100                                                                               50   90                                                                               50 60 90 70  100 100                                                                                20                                                                               100                                                                               20 --                               87A 95 100                                                                               30  100                                                                               80 70 80 95  100 100                                                                               100                                                                               100                                                                               70 --                               __________________________________________________________________________

                                      TABLE V-A                                    __________________________________________________________________________     Pre-Emergence Multi-weed Herbicide Test                                        Application Rate - 1.12 kg/ha                                                  Cmpd.                                                                          No. DB FT ARG WG SHC                                                                               WO BSG                                                                               AMG SESB                                                                               VL SP MD YNS                                                                               CB                               __________________________________________________________________________      82A                                                                               35 100                                                                               85  100                                                                                65                                                                               60 90 50  90   60                                                                               30  97                                                                               90 40                                85A                                                                               100                                                                               100                                                                               100 100                                                                               100                                                                               85 100                                                                               20  10  100                                                                               65 100                                                                               100                                                                               30                                92A                                                                               15  20                                                                               45  100                                                                                90                                                                               40 80 95  95  100                                                                               25 100                                                                               90 40                                93A                                                                               30  75                                                                               40  100                                                                               100                                                                               60 90 100 100 100                                                                               35 100                                                                               90 40                                94A                                                                               30  70                                                                               40  100                                                                               100                                                                               30 65 95  85  100                                                                                0 100                                                                               90 30                                95A                                                                                0  0  0   85                                                                                60                                                                               15 70 65  60  100                                                                               80  90                                                                               10 20                                96A                                                                               95 100                                                                               98  100                                                                               100                                                                               70 100                                                                               100 95   90                                                                               80 100                                                                               95 --                                97A                                                                               100                                                                               100                                                                               98  100                                                                               100                                                                               100                                                                               100                                                                               100 95  100                                                                               70 100                                                                               95 100                               98A                                                                               10  0  0   0  20                                                                               25 70  0  20   0  0  80                                                                               30 --                                99A                                                                               15  0  0   75                                                                                25                                                                                0 20 30  60   15                                                                               20  30                                                                               25  0                               100A                                                                                0  0  0   0  0  0 20 10   0   0  0  15                                                                                0 --                               101A                                                                               100                                                                                98                                                                               95  100                                                                               100                                                                               70 98 100 100 100                                                                               20 100                                                                               95 --                               102A                                                                               25  20                                                                               35  100                                                                               100                                                                               45 95 70  100 100                                                                               60 100                                                                               90 --                               103A                                                                               80  60                                                                               45  100                                                                               100                                                                               40 90 65  90  100                                                                                0 100                                                                               95  0                               106A                                                                               100                                                                               100                                                                               60   40                                                                                95                                                                               35 100                                                                               35  90  100                                                                               70 100                                                                               90 --                               107A                                                                               100                                                                               100                                                                               100 100                                                                               100                                                                               90 100                                                                               100 100 100                                                                               80 100                                                                               95 30                               108A                                                                               100                                                                               100                                                                               100 100                                                                               100                                                                               85 100                                                                               100 100 100                                                                               30 100                                                                               95 100                              109A.sup.a                                                                         65  20                                                                               85  100                                                                                98                                                                               60 90 30  50  100                                                                               50 100                                                                               90 100                              110A                                                                                0  60                                                                               30  100                                                                                65                                                                               25 65 25  30  100                                                                                0 100                                                                               60  0                               111A                                                                               100                                                                               100                                                                               100 100                                                                               100                                                                               75 98 100 100 100                                                                               90 100                                                                               -- 70                               112A                                                                               100                                                                               100                                                                               90  100                                                                               100                                                                               95 100                                                                               100 100 100                                                                               100                                                                               100                                                                               -- --                               113A                                                                               65  95                                                                               40  100                                                                               100                                                                               30 90 70  100 100                                                                                0 100                                                                               -- 30                               114A                                                                               70 100                                                                               25  100                                                                               100                                                                               40 100                                                                               100 100 100                                                                               30 100                                                                               95 80                               115A                                                                               100                                                                               100                                                                               100 100                                                                               100                                                                               100                                                                               100                                                                               100 100 100                                                                               45 100                                                                               85 100                              116A                                                                               25  15                                                                               20  100                                                                                65                                                                               35 65 45  50  100                                                                                0 100                                                                               95 10                               119A                                                                               100                                                                               100                                                                               100 100                                                                               100                                                                               100                                                                               100                                                                               100 100 100                                                                               95 100                                                                               95 90                               120A                                                                               100                                                                               100                                                                               100 100                                                                               100                                                                               95 100                                                                               100 100 100                                                                               100                                                                               100                                                                               90 100                              122A                                                                               80  80                                                                               45  100                                                                                60                                                                               65 70 100 100 100                                                                               100                                                                               100                                                                               90 100                              123A                                                                                0 100                                                                               50  100                                                                                85                                                                                0 60 100 90  100                                                                               80 100                                                                               100                                                                               20                               124A                                                                               25  50                                                                               65   90                                                                                65                                                                                0 40 75  80  100                                                                               40  90                                                                               80 60                               __________________________________________________________________________      .sup.a application rate was 0.56 kg/ha.                                  

                                      TABLE VII-A                                  __________________________________________________________________________     Post-Emergence Multi-weed Herbicide Test                                       Application Rate - 1.12 kg/ha                                                  Cmpd.                                                                          No. DB FT ARG WG SHC                                                                               WO BSG                                                                               AMG SESB                                                                               VL SP MD YNS                                                                               CB                               __________________________________________________________________________      82A                                                                               60 40 10  98 35 10 30  70 100 100                                                                               100                                                                                90                                                                               45 --                                85A                                                                               60 60 35  100                                                                               45 60 85  50 100 100                                                                               100                                                                               100                                                                               60 --                                92A                                                                               70 55 20  80 80 45 100                                                                                95  90  80                                                                               20  95                                                                               70 90                                93A                                                                               90 90 70  95 95 75 90  98  95  85                                                                               35 100                                                                               60 90                                94A                                                                               100                                                                               85 45  90 100                                                                               90 100                                                                               100  90  90                                                                               30 100                                                                               60 85                                95A                                                                               20 60  0  80 70  0 45  60  75  90                                                                                0  65                                                                               20 --                                96A                                                                               95 100                                                                               90  95 100                                                                               80 95 100 100 100                                                                               70 100                                                                               70 90                                97A                                                                               100                                                                               100                                                                               95  100                                                                               100                                                                               100                                                                               100                                                                               100 100 100                                                                               90 100                                                                               70 100                               98A                                                                               20  0  0  45 10 50 30  20  65 100                                                                                0  75                                                                               35 80                                99A                                                                               25 75 15  80 65 10 25  85 100 100                                                                               80 100                                                                               10 --                               100A                                                                               10 35  0  70 50  5 20  30  70  40                                                                                0 100                                                                               10 100                              101A                                                                               30 60 25  100                                                                               60 60 80 100 100 100                                                                               30 100                                                                               70 --                               103A                                                                               90 100                                                                               25  100                                                                               100                                                                               80 100                                                                               100 100 100                                                                               15 100                                                                               40 --                               104A                                                                               98 98 25  98 100                                                                               15 100                                                                               100 100 100                                                                               60 100                                                                               95 --                               106A                                                                               75 90 30  90 70 25 100                                                                               100 100 100                                                                               80 100                                                                               75 --                               107A                                                                               100                                                                               100                                                                               80  90 85 100                                                                               100                                                                               100 100 100                                                                               60 100                                                                               40 --                               108A                                                                               100                                                                               100                                                                               65  90 60 95 100                                                                               100 100 100                                                                               90 100                                                                               90 --                               109A.sup.a                                                                         90 60 45  90 70 60 98  95  95 100                                                                               98  80                                                                               55 --                               110A                                                                               50 50 20  100                                                                               50 10 40 100  98  98                                                                               20 100                                                                               35 45                               111A                                                                               85 90 80  90 70 60 95 100  90 100                                                                               65 100                                                                               80 60                               112A                                                                               100                                                                               100                                                                               90  100                                                                               100                                                                               95 100                                                                               100 100 100                                                                               45 100                                                                               95 70                               113A                                                                               70 50 20  90 60 50 80  95  95 100                                                                               60 100                                                                               -- 60                               114A                                                                               85 100                                                                               15  100                                                                               100                                                                               60 00 100 100 100                                                                               100                                                                               100                                                                               60 --                               115A                                                                               100                                                                               100                                                                               45  100                                                                               100                                                                               80 100                                                                               100 100 100                                                                               100                                                                               100                                                                               90 --                               116A                                                                               80 60 25  90 35 40 45  75  90 100                                                                               40  90                                                                               75 60                               119A                                                                               60 70 30  95 70 20 90 100 100 100                                                                               90 100                                                                               30 85                               120A                                                                               75 90 60  95 80 45 100                                                                               100  90 100                                                                               65 100                                                                               35 100                              122A                                                                               60 90 15  100                                                                               30 15 15 100 100 100                                                                               75 100                                                                               45 95                               123A                                                                                0 100                                                                               35  100                                                                               50 15 85 100 100 100                                                                               100                                                                               100                                                                               70 85                               124A                                                                               25 100                                                                               35  40 35  0 40  95 100 100                                                                               100                                                                               100                                                                               85 75                               __________________________________________________________________________      .sup.a Application rate was 0.56 kg/ha.                                        A dash mark (--) is used in Tables II-VII to indicate that no percent          control number was available.                                            

                                      TABLE IV-B                                   __________________________________________________________________________     Pre-Emergence Multi-Weed Herbicide Test                                        Application Rate - 2.24 kg/ha                                                  Cmpd.                                                                          No. DB FT ARG WG SHC                                                                               WO BSG                                                                               AMG SESB                                                                               VL SP                                                                               MD YNS                                                                               CB                                __________________________________________________________________________     14B 80 100                                                                               100 100                                                                               100                                                                               80 95  70  60 100                                                                               40                                                                                85                                                                               100                                                                               10                                21B 85 100                                                                               90  100                                                                               100                                                                               85 100                                                                               100 100 100                                                                               70                                                                               100                                                                               95 100                               24B 100                                                                               100                                                                               100 100                                                                               100                                                                               100                                                                               100                                                                               100 100 100                                                                               75                                                                               100                                                                               95 --                                38B 100                                                                               100                                                                               100 100                                                                               100                                                                               100                                                                               100                                                                                20  10 100                                                                               20                                                                                95                                                                               100                                                                               20                                88B 75 100                                                                               60  100                                                                               100                                                                               70 60  20  40 100                                                                                0                                                                               100                                                                               60 20                                89B 20  60                                                                               30   85                                                                                95                                                                               55 40  15  20  65                                                                                0                                                                               100                                                                               35 50                                90B 60 100                                                                               60  100                                                                               100                                                                               45 30 100 100 100                                                                               15                                                                               100                                                                               50 85                                103B                                                                               95 100                                                                               75  100                                                                               100                                                                               50 85 100 100 100                                                                               80                                                                               100                                                                               80 40                                104B                                                                               60 100                                                                               60  100                                                                               100                                                                               45 30 100 100 100                                                                               15                                                                               100                                                                               50 85                                __________________________________________________________________________      (--) = Specie did not germinate for some reason.                         

                                      TABLE V-B                                    __________________________________________________________________________     Post-Emergence Multi-Weed Herbicde Test                                        Application Rate - 2.24 kg/ha                                                  Cmpd.                                                                          No. DB FT ARG WG SHC                                                                               WO BSG                                                                               AMG SESB                                                                               VL SP                                                                               MD YNS                                                                               CB                                __________________________________________________________________________     24B 35  25                                                                               45   60                                                                               65 85 90 100 100 -- 90                                                                               100                                                                               65 --                                88B 60  30                                                                               30   90                                                                               100                                                                               80 100                                                                               100 100 100                                                                               30                                                                               100                                                                               20 100                               89B 50  70                                                                               35   90                                                                               60 35 20 100  90 100                                                                               35                                                                               100                                                                               15 100                               90B 30 100                                                                               40  100                                                                               70 10 25 100 100 100                                                                               30                                                                                90                                                                               50  95                               103B                                                                               95 100                                                                               70  100                                                                               65 75 65 100 100 100                                                                               65                                                                               100                                                                               50 100                               104B                                                                               30 100                                                                               40  100                                                                               70 10 25 100 100 100                                                                               30                                                                                90                                                                               50  95                               __________________________________________________________________________      (--) = Specie dd not germinate for some reason.                          

                                      TABLE VI-B                                   __________________________________________________________________________     Pre-Emergence Multi-Weed Herbicide Test                                        Application Rate - 1.12 kg/ha                                                  Cmpd.                                                                          No.  DB FT ARG WG SHC WO BSG                                                                               AMG SESB                                                                               VL SP MD YNS                                                                               CB                             __________________________________________________________________________      1B  25  10                                                                               30   85                                                                                55  0 --  55 --  100                                                                               --  75                                                                               75 35                             23B  55  95                                                                               90  100                                                                                95*                                                                               95 95  98 80  -- 10 100                                                                               95 --                             68B  65 100                                                                               60  100                                                                                100*                                                                               6 90 100 90  100                                                                               20 100                                                                               30 40                             69B  70 100                                                                               60  100                                                                                100*                                                                              95 95 100 95  100                                                                                0 100                                                                               85 25                             70B  60 100                                                                               75  100                                                                                100*                                                                              85 100                                                                               100 90  100                                                                               25 100                                                                               90 25                             76B  100                                                                               100                                                                               85  100                                                                               100*                                                                               85 98 100 95  -- 35 100                                                                               95 --                             78B  40  70                                                                               15   95                                                                                75*                                                                               25 80  65 75  --  0 100                                                                               80 --                             79B  100                                                                               100                                                                               100 100                                                                               100 98 100                                                                               100 85  100                                                                               85 100                                                                               95 --                             80B  98 100                                                                               95  100                                                                               100 60 98  99 90  100                                                                               35 100                                                                               85 --                             83B  20 100                                                                               60  100                                                                                100*                                                                              40 90  85 65  100                                                                                0 100                                                                               85 --                             84B   0  90                                                                               25   98                                                                                100*                                                                              30 90  20 35  100                                                                                5 100                                                                               50 --                             85B  80 100                                                                               50  100                                                                               100 60 90 100 90  100                                                                                0 100                                                                               95 --                             86B  60  90                                                                               40  100                                                                               100 60 70  35 60  100                                                                               100                                                                               100                                                                               -- --                             87B   0  90                                                                               15  100                                                                                85 15 70  40 60  100                                                                               40  90                                                                               20 --                             92B  20  40                                                                               10   95                                                                                40 10 60  65 30  100                                                                                0  55                                                                               60  0                             93B  60  95                                                                               20  100                                                                               100 75 100                                                                               100 100 100                                                                                0 100                                                                               40 35                             94B   0  80                                                                               40  100                                                                                95 25 85  80 40  100                                                                               10  85                                                                               55 10                             95B  98 100                                                                               30  100                                                                               100 40 90 100 100 100                                                                               40 100                                                                               90 30                             96B  100                                                                               100                                                                               75  100                                                                               100 95 100                                                                               100 100 100                                                                               60 100                                                                               85 100                            97B  100                                                                               100                                                                               90  100                                                                               100 95 100                                                                               100 100 100                                                                               60 100                                                                               95 100                            98B  95 100                                                                               100 100                                                                               100 80 100                                                                               100 100 100                                                                               50 100                                                                               100                                                                               60                              99B**                                                                              -- 100                                                                               75  100                                                                                100*                                                                              20 75  50 75   95                                                                                0 -- 85 30                             100B 100                                                                                98                                                                               98  100                                                                               100 90 95 100 75  100                                                                               70 100                                                                               95 40                             102B  0 100                                                                               25  100                                                                                90 75 95  60 60  100                                                                               30 100                                                                               90 --                             __________________________________________________________________________      *seedling johnsongrass (Sroghum halepense) was substituted for roxorgange      sorghum.                                                                       **Application rate was 0.56 kg/ha                                              (--) = Specie did not germinate for some reason.                         

                                      TABLE VII-B                                  __________________________________________________________________________     Post-Emergence Multi-Weed Herbicide Test                                       Application Rate - 1.12 kg/ha                                                  Cmpd.                                                                          No.  DB FT ARG WG SHC                                                                               WO BSG                                                                               AMG SESB                                                                               VL SP MD YNS                                                                               CB                              __________________________________________________________________________      1B  45 35 40  90 35 10 --  60 --   75                                                                               --  60                                                                               50 55                              23B  90 100                                                                               80  90  90*                                                                              90 90  80  90  90                                                                               40  70                                                                               25 --                              68B  50 60 40  85  80*                                                                              75 100                                                                                95  90  85                                                                               55 100                                                                               40 --                              69B  70 80 35  90  90*                                                                              80 90  80  85  90                                                                               20  90                                                                               25 --                              70B  100                                                                               90 80  100                                                                               100*                                                                              95 100                                                                               100  95  80                                                                               30  75                                                                               45 90                              76B  100                                                                               100                                                                               98  100                                                                               100* 100                                                                          100                                                                               100                                                                               100 100 60 100                                                                               40 --                                 78B  100                                                                               90 80  85 100*                                                                              70 90 100 100 100                                                                                0  90                                                                               45 --                              79B  80 35 45  70  60*                                                                              70 70  45  98 100                                                                               35  90                                                                               20 --                              80B  60 70 25  90  60*                                                                              60 85  70 90  100                                                                               15 100                                                                               25 100                             85B  95 100                                                                               65  100                                                                               80 90 100                                                                               100 100 100                                                                               25 100                                                                               85 --                              86B  30 60 20  75 50 50 60  50  65 100                                                                               10 100                                                                               20 80                              87B   0  0  0  100                                                                               45 20 30  60  90  80                                                                                0 100                                                                               30 45                              92B  20 80 10  85 15  0 30 100  40 100                                                                                0  60                                                                               60 30                              93B  70 100                                                                               25  100                                                                               100                                                                               85 100                                                                               100 100 100                                                                               100                                                                               100                                                                               80 --                              94B  20 70 30  90 80 30 20 100 100 100                                                                               60  30                                                                               30 100                             95B  60 90 15  95 95 25 90 100 100 100                                                                               75 100                                                                               70 100                             96B  50 80  0  90 70 30 100                                                                               100 100 100                                                                               40 100                                                                               20 100                             97B  65 100                                                                               35  100                                                                               75 70 80 100 100 100                                                                               50 100                                                                               50 100                             98B  95 100                                                                               65  95 90 100                                                                               95 100 100  90                                                                               40  80                                                                               60 95                               99B**                                                                              -- 100                                                                               95  90  90*                                                                              90 100                                                                                25  80  40                                                                               100                                                                               -- 35 75                              100B 65 75 60  80 75 60 85 100 100 100                                                                               45 100                                                                               65 60                              102B 30 75 20  80 60  0 40  70 100 100                                                                               30 100                                                                               75 --                              __________________________________________________________________________      *=Seedling johnsongram (Sorghum halepense) was substituted for roxorange       sorghum.                                                                       **=Application rate was 0.56 kg/ha.                                            (--)=Specie did not germinate for some reason.                           

                                      TABLE IV-C                                   __________________________________________________________________________     Pre-Emergence Multi-weed Herbicide Test                                        Application Rate - 1.12 kg/ha                                                  Cmpd.                                                                          No. DB FT ARG WG SHC                                                                               WO BSG                                                                               AMG SESB                                                                               VL SP MD YNS                                                                               CB                               __________________________________________________________________________     2C  0  100                                                                               0   100                                                                               -- 45 70 65  50  100                                                                               15 100                                                                               90 --                               __________________________________________________________________________      (--) = Not tested.                                                       

                                      TABLE V-C                                    __________________________________________________________________________     Post-Emergence Multi-Weed Herbicidal Activity                                  Application Rate - 1.12 kg/ha                                                  Cmpd.                                                                          No. DB FT ARG WG SHC                                                                               WO BSG                                                                               AMG SESB                                                                               VL SP MD YNS                                                                               CB                               __________________________________________________________________________     2D  0  30 0   100                                                                               -- 0  60 85  95  100                                                                               100                                                                               90 40 --                               __________________________________________________________________________      (--) = Not tested.                                                       

                                      TABLE IV-D                                   __________________________________________________________________________     Pre-Emergence Multi-weed Herbicide Test                                        Application Rate - 2.24 kg/ha                                                  Cmpd.                                                                          No. DB FT ARG WG SHC                                                                               WO BSG                                                                               AMG SESB                                                                               VL SP MD YNS                                                                               CB                               __________________________________________________________________________      7D 100                                                                               100                                                                               100 100                                                                               100                                                                               100                                                                               100                                                                               100 100 100                                                                               100                                                                               100                                                                               95 100                               8D 100                                                                               100                                                                               100 100                                                                               100                                                                               100                                                                               100                                                                               100 100 100                                                                               100                                                                               100                                                                               95 --                               16D.sup.a                                                                           70                                                                               100                                                                                65 100                                                                               100                                                                               60 98  55 100 100                                                                                90                                                                               100                                                                               90 --                               24D 100                                                                               100                                                                               100 100                                                                               100                                                                               100                                                                               100                                                                               100 100 100                                                                               100                                                                               100                                                                               100                                                                               --                               29D 100                                                                               100                                                                               100 100                                                                               100                                                                               100                                                                               100                                                                               100 100 100                                                                                30                                                                               100                                                                               95  80                              33D  75                                                                                15                                                                                60  90                                                                                90                                                                               20 95 100 100 100                                                                                60                                                                               100                                                                               95 100                              53D 100                                                                               100                                                                               100 100                                                                               100                                                                               90 100                                                                               100 100 100                                                                               100                                                                               100                                                                               95 100                              57D 100                                                                               100                                                                                25 100                                                                               100                                                                               30 25 100 100 100                                                                               100                                                                               100                                                                               95 100                              64D.sup.a                                                                          --  0  0   95                                                                                35                                                                                0 15  50  75  75                                                                                25                                                                               -- 75  40                              66D.sup.a                                                                          --  0  15  15                                                                                50                                                                               20 50 100 100  75                                                                                0 -- 90 100                              67D.sup.a                                                                          --  0  0  100                                                                               100                                                                                0 25  95  75  50                                                                                25                                                                               -- 30  75                              69D.sup.a                                                                          --  30                                                                                0  100                                                                               100                                                                                0 70 100 100 100                                                                                35                                                                               -- 95 100                              70D.sup.a                                                                          -- 100                                                                                10 100                                                                               100                                                                               25 65 100 100 100                                                                                0 -- 95 100                              __________________________________________________________________________      (--) = Not tested.                                                             .sup.a = Tested at 0.28 kg/ha.                                           

                                      TABLE V-D                                    __________________________________________________________________________     Pre-Emergence Multi-weed Herbicide Test                                        Application Rate - 1.12 kg/ha                                                  Cmpd.                                                                          No. DB FT ARG WG SHC                                                                               WO BSG                                                                               AMG SESB                                                                               VL SP MD YNS                                                                               CB                               __________________________________________________________________________     34D  90                                                                                85                                                                               30   95                                                                               -- 45  98                                                                                75 100 100                                                                               40 100                                                                               50 --                               35D 100                                                                                85                                                                               70  100                                                                               -- 90 100                                                                               100 100 100                                                                               40 100                                                                               75 --                               40D 100                                                                               100                                                                               20  100                                                                               -- 70 100                                                                                98  98 100                                                                               20 100                                                                               50 --                               41D 100                                                                               100                                                                               80  100                                                                               -- 60 100                                                                               100 100 100                                                                               25 100                                                                               95 --                               42D  50                                                                                60                                                                               40   85                                                                               -- 30 100                                                                               100 100 100                                                                               100                                                                               100                                                                               90 --                               43D  90                                                                                95                                                                               60  100                                                                               -- 30  98                                                                               100  98 100                                                                               45 100                                                                               95 --                               44D  60                                                                               100                                                                               20  100                                                                               -- 60 100                                                                               100  90 100                                                                               20 100                                                                               80 --                               45D  95                                                                               100                                                                               35  100                                                                               -- 60  90                                                                               100 100 100                                                                                0 100                                                                               90 --                               46D 100                                                                               100                                                                               90  100                                                                               -- 95 100                                                                               100 100 100                                                                               40 100                                                                               95 --                               47D 100                                                                               100                                                                               100 100                                                                               -- 98 100                                                                               100  98 100                                                                               30 100                                                                               95 --                               48D 100                                                                               100                                                                               100 100                                                                               -- 100                                                                               100                                                                               100 100 100                                                                               90 100                                                                               100                                                                               --                               49D 100                                                                               100                                                                               100 100                                                                               -- 100                                                                               100                                                                               100 100 100                                                                               90 100                                                                               -- --                               50D 100                                                                               100                                                                               100 100                                                                               100                                                                               85 100                                                                               100 100 100                                                                               90 100                                                                               98 --                               54D 100                                                                               100                                                                               85  100                                                                               100                                                                               15 100                                                                                25 100 100                                                                               65 100                                                                               95 100                              55D  85                                                                               100                                                                               35  100                                                                                98                                                                               15 100                                                                                15 100 100                                                                               65 100                                                                               95 --                               56D 100                                                                               100                                                                               100 100                                                                               100                                                                               100                                                                               100                                                                               100 100 100                                                                               100                                                                               100                                                                               100                                                                               100                              58D  98                                                                               100                                                                               40   95                                                                                40                                                                               20  95                                                                               100 100 100                                                                               85 100                                                                               100                                                                               95                               59D 100                                                                               100                                                                               100 100                                                                               100                                                                               90 100                                                                               100 100 100                                                                               100                                                                               100                                                                               85 80                               60D 100                                                                               100                                                                               100 100                                                                               100                                                                               100                                                                               100                                                                               100 100 100                                                                               75 100                                                                               85 80                               __________________________________________________________________________      (--) = Not tested.                                                       

                                      TABLE VI-D                                   __________________________________________________________________________     Pre-Emergence Multi-weed Herbicide Test                                        Application Rate - 0.56 kg/ha                                                  Cmd.                                                                           No. DB FT ARG WG SHC                                                                               WO BSG                                                                               AMG SESB                                                                               VL SP MD YNS                                                                               CB                               __________________________________________________________________________     61D -- 100                                                                               65  100                                                                               65 20  80                                                                               20  40   80                                                                               10 -- 20  0                               62D -- 50 35   70                                                                               50  0  0  0  25   50                                                                                0 --  0  0                               63D 100                                                                               100                                                                               100 100                                                                               100                                                                               95 100                                                                               90  95  100                                                                               75 100                                                                               100                                                                               85                               68D --  0 20   0  0  0  0 60  100 100                                                                               90 -- 75 75                               71D -- 50 40   50                                                                               75 40  35                                                                               75  50   70                                                                                0 -- 75 75                               72D -- 35 60  100                                                                               85 50 100                                                                               25  65  100                                                                               35 -- 100                                                                               35                               73D -- 90 70  100                                                                               95 25  0 70  100 100                                                                                0 -- 50 25                               __________________________________________________________________________      (--) = Not tested.                                                       

                                      TABLE VII-D                                  __________________________________________________________________________     Post-Emergence Multi-Weed Herbicidal Activity                                  Application Rate -- 2.24 kg/ha                                                 Cmd.                                                                           No. DB FT ARG WG SHC                                                                               WO BSG                                                                               AMG SESB                                                                               VL SP MD YNS                                                                               CB                               __________________________________________________________________________      7D 100                                                                               100                                                                               100 100                                                                               80  90                                                                                10                                                                                95 100 100                                                                               55 100                                                                               45 100                              16D.sup.a                                                                          100                                                                                85                                                                               35  100                                                                               100                                                                               100                                                                               100                                                                               100 100 100                                                                               100                                                                               100                                                                               85  70                              24D 100                                                                               100                                                                               100 100                                                                               100                                                                               100                                                                               100                                                                               100 100 100                                                                               100                                                                               100                                                                               100                                                                               --                               29D 100                                                                               100                                                                               60  100                                                                               90 100                                                                               100                                                                               100 100 100                                                                               100                                                                               100                                                                               100                                                                               --                               33D  90                                                                                98                                                                               85  100                                                                               100                                                                                80                                                                               100                                                                               100 100 100                                                                               90 100                                                                               90 100                              53D 100                                                                               100                                                                               60  100                                                                               100                                                                               100                                                                               100                                                                               100 100 100                                                                               100                                                                               100                                                                               100                                                                               --                               57D  25                                                                                40                                                                               10  100                                                                               10  0  10                                                                               100  95 100                                                                               35 100                                                                               -- 100                              64D.sup.a                                                                          --  0  0   90                                                                                0  0  85                                                                                40 100  80                                                                               50 -- 35 100                              66D.sup.a                                                                          --  0  0   65                                                                                0  0  70                                                                                75  80  75                                                                                0 -- 25  75                              67D.sup.a                                                                          --  0  0   75                                                                               35  0  40                                                                                70  80  60                                                                                0 --  0 100                              69D.sup.a                                                                          --  0  0   80                                                                               35  0 100                                                                                90 100 100                                                                               40 -- 35 100                              70D.sup.a                                                                          -- 100                                                                                0  100                                                                               70  90                                                                                90                                                                               100 100 100                                                                               30 -- 25 100                              __________________________________________________________________________      (--) = Not tested.                                                             .sup.(a) = Tested at 0.28 kg/ha.                                         

                                      TABLE VIII-D                                 __________________________________________________________________________     Post-Emergence Multi-weed Herbicide Test                                       Application Rate - 1.12 kg/ha                                                  Cmd.                                                                           No. DB FT ARG WG SHC                                                                               WO BSG                                                                               AMG SESB                                                                               VL SP MD YNS                                                                               CB                               __________________________________________________________________________     34D 90  85                                                                               30   95                                                                               -- 45 98  75 100 100                                                                               40 100                                                                               50 --                               35D 100                                                                                85                                                                               70  100                                                                               -- 90 100                                                                               100 100 100                                                                               40 100                                                                               75 --                               40D 75 100                                                                                5  100                                                                               -- 50 75 100 100 100                                                                               40 100                                                                               30 --                               41D--                                                                              -- -- --  -- -- -- -- --  --  -- -- -- -- --                               42D 40 100                                                                               35  100                                                                               -- 50 80 100 100 100                                                                               80 100                                                                               70 --                               43D 60  70                                                                               20  100                                                                               -- 55 60 100 100 100                                                                               95 100                                                                               70 --                               44D -- -- --  -- -- -- -- --  --  -- -- -- -- --                               45D -- -- --  -- -- -- -- --  --  -- -- -- -- --                               46D -- -- --  -- -- -- -- --  --  -- -- -- -- --                               47D 90 100                                                                               35  100                                                                               -- 75 90 100 100 100                                                                               25 100                                                                               45 --                               48D 80 100                                                                               60  100                                                                               -- 60 80 100 100 100                                                                               85 100                                                                               60 --                               49D -- -- --  -- -- -- -- --  --  -- -- -- -- --                               50D 90  80                                                                               60   95                                                                               80 90 100                                                                               100 100 100                                                                               65 100                                                                               80 --                               54D 35  50                                                                               30  100                                                                               30 15 90 100 100 100                                                                               100                                                                               100                                                                               95 --                               55D 100                                                                               100                                                                               20  100                                                                               90 20 100                                                                                90 100 100                                                                               100                                                                               100                                                                               -- --                               56D 75  90                                                                               75   95                                                                               90 25 100                                                                               100 100 100                                                                               90 100                                                                               90 100                              58D 70 100                                                                               40  100                                                                               95 30 95 100  95 100                                                                               95 100                                                                               95  85                              59D 90 100                                                                               95  100                                                                               100                                                                               50 100                                                                               100 100 100                                                                               95 100                                                                               100                                                                                95                              60D 95 100                                                                               100 100                                                                               100                                                                               75 95 100 100 100                                                                               95 100                                                                               100                                                                               100                              __________________________________________________________________________      (--) = Not tested.                                                       

                                      TABLE IX-D                                   __________________________________________________________________________     Post-Emergence Multi-weed Herbicide Test                                       Application Rate - 0.56 kg/ha                                                  Cmd.                                                                           No. DB FT ARG WG SHC                                                                               WO BSG                                                                               AMG SESB                                                                               VL SP MD YNS                                                                               CB                               __________________________________________________________________________     61D -- 40  0  50 35  0 40 75  95  100                                                                                0 -- 25  50                              62D -- 35  0  20  0  0 20 35  60  100                                                                                0 --  0 100                              63D 100                                                                               100                                                                               85  98 85 100                                                                               100                                                                               100 100 100                                                                               100                                                                               85 85  95                              68D -- 30 40  85  0 25 60 80  95  100                                                                               95 --  0  80                              71D -- 50  0  80 65  0 75 100 80  100                                                                               50 -- 25 100                              72D -- 90 70  80 50 50 75 85  100 100                                                                               90 -- 100                                                                               100                              73D -- 100                                                                               15  100                                                                               75 75 85 100 100  90                                                                               60 -- 80 100                              __________________________________________________________________________      (--) = Not tested.                                                       

                                      TABLE IV-E                                   __________________________________________________________________________     Pre-Emergence Multi-weed Herbicide Test                                        Application Rate - 2.24 kg/ha                                                  Cmd.                                                                           No. DB FT ARG WG JG WO BSG                                                                               AMG SESB                                                                              VL SP                                                                               MD YNS                                   __________________________________________________________________________     17E 95 85 35  100                                                                               85                                                                               25 90 100 100 100                                                                               40                                                                               100                                                                               95                                    18E  0  0  0   50                                                                               20                                                                                0 15  60  45 100                                                                                0                                                                               100                                                                               --                                    __________________________________________________________________________

                                      TABLE V-E                                    __________________________________________________________________________     Pre-Emergence Multi-weed Herbicide Test                                        Application Rate - 1.12 kg/ha                                                  Cmd.                                                                           No. DB FT ARG WG JG WO BSG                                                                               AMG SESB                                                                               VL SP MD YNS                                 __________________________________________________________________________      7E 30 70 20  100                                                                               75  0 90 100 95  100                                                                               100                                                                               100                                                                               90                                   8E 95 95 45  100                                                                               98 25 90 100 95  100                                                                               90 100                                                                               90                                   9E 10 70 40  100                                                                               20  0 80 100 85  100                                                                               40 100                                                                               95                                  10E 100                                                                               100                                                                               10  100                                                                               40  0 90 100 100 100                                                                               80 100                                                                               100                                 11E 90 100                                                                               90  100                                                                               100                                                                               65 100                                                                               100 90  100                                                                               30 100                                                                               65                                  12E 100                                                                               100                                                                               80  100                                                                               100                                                                               85 90 100 100 100                                                                               85 100                                                                               90                                  13E  0 100                                                                               10  100                                                                               100                                                                               80 70  80 90  100                                                                               70 100"                                                                              80                                  15E  0 10  0   90                                                                                0   0                                                                               15  35 30  100                                                                               10  85                                                                               75                                  19E 100                                                                               90  0  100                                                                               20 10 40  95 100 100                                                                               100                                                                               100                                                                               65                                  __________________________________________________________________________

                                      TABLE VI-E                                   __________________________________________________________________________     Pre-Emergence Multi-weed Herbicide Test                                        Application Rate - 2.24 kg/ha                                                  Cmd.                                                                           No. DB FT ARG WG JG                                                                               WO BSG                                                                               AMG SESB                                                                               VL SP                                                                               MD YNS                                   __________________________________________________________________________     17E 80 100                                                                               55  95 90                                                                               20 60 100 100 100                                                                               75                                                                               100                                                                               70                                    18E  0 100                                                                                0  98 20                                                                                0 10  70  60 100                                                                               10                                                                               100                                                                               45                                    __________________________________________________________________________

                                      TABLE VII-E                                  __________________________________________________________________________     Post-Emergence Multi-Weed Herbicidal Activity                                  Application Rate - 1.12 kg/ha                                                  Cmpd.                                                                          No. DB FT ARG WG JG WO BSG                                                                               AMG SESB                                                                               VL SP MD YNS                                 __________________________________________________________________________      7E 25 30  0  70 60 20 90 75   95  85                                                                               50 100                                                                               35                                   8E 80 80 20  70 70 40 80 50   80  80                                                                               60 60 35                                   9E  0 30  0  75 15 25 100                                                                               95  100 100                                                                               60 100                                                                               25                                  10E 60 80 20  70 35 25 80 75   90  90                                                                               70 100                                                                               45                                  11E 45 100                                                                               20  100                                                                               100                                                                               40 50 100 100 100                                                                               20 100                                                                               35                                  12E 70 60 30  100                                                                               100                                                                               80 98 90  100 100                                                                               70 98 40                                  13E 25 100                                                                               10  100                                                                               100                                                                               85 100                                                                               80  100 100                                                                               10 90 25                                  15E 30 65 10  90 50 30 20 85   80  98                                                                               30 65 15                                  19E 20 60 10  90 10 15 90 100 100  70                                                                               100                                                                               40 85                                  __________________________________________________________________________

                                      TABLE IV-F                                   __________________________________________________________________________     Pre-Emergence Multi-weed Herbicide Test                                        Application Rate - 1.12 kg/ha                                                  Cmpd.                                                                          No. DB FT ARG WG JG WO BSG                                                                               AMG SESB                                                                               VL SP MD YNS                                                                               CB                               __________________________________________________________________________     19F 40 35 60  100                                                                               90 30 90 100 100 -- 20 100                                                                               90 --                               26F 25 70 45  95 60 25 85 35  75  -- 20 100                                                                               95 90                               27F 45 65 40  100                                                                               60 25 80 100 85  100                                                                               40 100                                                                               95 35                               28F 80 100                                                                               90  100                                                                               100                                                                               90 100                                                                               70  90  100                                                                               30 100                                                                               95 35                               29F 90 45 75  100                                                                               85 40 90 95  90  100                                                                               40 100                                                                               95 --                               30F 90 45 75  100                                                                               90 75 100                                                                               100 80  100                                                                               60 100                                                                               95 --                               31F 60 65 75  100                                                                               100                                                                               55 95 100 100 100                                                                               100                                                                               100                                                                               95 --                               32F 90 100                                                                               90  100                                                                               100                                                                               65 85 100 90  100                                                                               95 100                                                                               85 --                               33F 100                                                                               100                                                                               95  100                                                                               100                                                                               95 100                                                                               100 100 100                                                                               25 100                                                                               90 --                               35F 90 100                                                                               100 100                                                                               -- 90 90 100 90  100                                                                               10 100                                                                               75 --                               36F 90 35 85  100                                                                               -- 15 80 95  90  100                                                                               50 100                                                                               95 --                               39F 100                                                                               100                                                                               100 100                                                                               100                                                                               95 100                                                                               100 100 100                                                                               100                                                                               100                                                                               98 --                               40F 100                                                                               100                                                                               80  100                                                                               100                                                                               70 100                                                                               100 100 100                                                                               90 100                                                                               95 --                               41F 100                                                                               100                                                                               100 100                                                                               100                                                                               100                                                                               100                                                                               100 100 100                                                                               60 100                                                                               98 --                               42F 60 100                                                                               85  100                                                                               100                                                                               70 95 100 95  100                                                                               10 100                                                                               95 50                               43F 85 100                                                                               25  100                                                                               60 25 98 100 100 100                                                                               100                                                                               100                                                                               90 100                              44F 0  80 10  85 0  0  75 0   30  100                                                                               0  100                                                                               0  10                               45F 25 100                                                                               40  100                                                                               60 0  65 60  60  100                                                                               50 100                                                                               70 0                                50F -- 100                                                                               50  100                                                                               35 35 75     100 100                                                                               --                                        __________________________________________________________________________      (--) = Not tested.                                                       

                                      TABLE V-F                                    __________________________________________________________________________     Pre-Emergence Multi-weed Herbicide Test                                        Application Rate - 0.56 kg/ha                                                  Cmpd.                                                                          No. DB FT ARG WG JG WO BSG                                                                               AMG SESB                                                                               VL SP                                                                               MD YNS                                                                               CB                                __________________________________________________________________________     46F 0  65 35  75 65 0   0  0  35  100                                                                               25                                                                               90 80  0                                47F -- 60 35  100                                                                               100                                                                               0  90 100 100 100                                                                               70                                                                               -- 100                                                                               75                                48F -- 75 20  90 60 0  15 70  35  90 0 -- 20 40                                49F -- 60 10  100                                                                               60 0  50 100 95  100                                                                               40                                                                               -- 90 100                               51F -- 40 10  95 40 10 50 65  100 100                                                                               0 -- 95 65                                __________________________________________________________________________      (--)  Not tested.                                                        

                                      TABLE VI-F                                   __________________________________________________________________________     Post-Emergence Multi-Weed Herbicidal Activity                                  Application Rate - 2.24 kg/ha                                                  Cmpd.                                                                          No. DB FT ARG WG JG WO BSG                                                                               AMG SESB                                                                               VL SP MD YNS                                                                               CB                               __________________________________________________________________________     19F 100                                                                               90 65  100                                                                               100                                                                               98 100                                                                               100 100 100                                                                               60 100                                                                               70 100                              26F 60 75 60  95 45 50 90 50  90  100                                                                               40 90 60 --                               27F 80 70 65  95 100                                                                               90 100                                                                               100 100 100                                                                               85 100                                                                               75 --                               28F 80 100                                                                               75  90 85 80 100                                                                               80  80  100                                                                               30 100                                                                               85 85                               29F 85 70 55  90 98 90 100                                                                               100 100 100                                                                               35 100                                                                               60 100                              30F 90 80 40  90 85 80 80 70  100 100                                                                               20 100                                                                               40 --                               31F 100                                                                               80 20  100                                                                               100                                                                               100                                                                               100                                                                               100 100 100                                                                               100                                                                               100                                                                               85 --                               32F 70 90 60  100                                                                               100                                                                               98 100                                                                               100 100 100                                                                               100                                                                               100                                                                               60 --                               33F 95 100                                                                               80  100                                                                               90 100                                                                               100                                                                               100 100 100                                                                               70 100                                                                               40 --                               35F 70 90 40  100                                                                               -- 100                                                                               100                                                                               100 100 100                                                                               98 100                                                                               30 --                               36F 85 100                                                                            35 100 -- 20 100                                                                               100                                                                               100 100 100                                                                               100                                                                               15 --                                  39F 100 100                                                                           85 100 100                                                                               100                                                                               100                                                                               100                                                                               100 100 100                                                                               100                                                                               90 100                                 40F 100 100                                                                           30 100 100                                                                               100                                                                               100                                                                               100                                                                               100 100 90 100                                                                               75 --                                  41F 100 100                                                                           35 90  70 100                                                                               90 100                                                                               100 100 50 100                                                                               70 --                                  42F 45 100                                                                               50  100                                                                               70 55 80 100 100 100                                                                               70 100                                                                               75 100                              43F 25 80 15  98 35 0  20 100 100 100                                                                               100                                                                               100                                                                               60 95                               44F 0  15 0   65 0  0  0  70  100 100                                                                               40 100                                                                               0  100                              45F 0  75 35  70 35 0  60 50  85  100                                                                               50 100                                                                               75 70                               50F -- 40 0   75 45 40 60 100 100 95 30 -- 60 100                              __________________________________________________________________________      (--) = Not tested.                                                       

                                      TABLE VII-F                                  __________________________________________________________________________     Post-Emergence Multi-Weed Herbicidal Activity                                  Application Rate - 0.56 kg/ha                                                  Cmd.                                                                           No. DB FT ARG WG JG                                                                               WO BSG                                                                               AMG SESB                                                                               VL SP                                                                               MD YNS                                                                               CB                                 __________________________________________________________________________     46F 25 35 20  50 35                                                                               35  0 20   75 100                                                                               35                                                                               95 -- 50                                 47F -- 75 25  90 40                                                                               25 80 100 100 100                                                                               80                                                                               -- 75 100                                48F -- 50 35  80 35                                                                               40 0  75  100 85 15                                                                               -- 50 75                                 49F -- 35 0   75 30                                                                               0  20 100 100 100                                                                               80                                                                               -- 25 85                                 51F -- 35 0   80 35                                                                               20 70 50  95  95 25                                                                               -- 65 50                                 __________________________________________________________________________      (--) = Not Tested.                                                       

The compounds of the present invention and their salts are useful as herbicides and can be applied in a variety of ways at various concentrations. In practice, the compounds or salts are formulated into herbicidal compositions, by admixture, in herbicidally effective amounts, with the adjuvants and carriers normally employed for facilitating the dispersion of active ingredients for agricultural applications, recognizing the fact that the formulation and mode of application of a toxicant may affect the activity of the materials in a given application. Thus, these active herbicidal compounds or salts can be formulated as graules of relatively large particle size, as wettable powders, as emulsifiable concentrates, as powdery dusts, as flowables, as solutions or as any of several other known types of formulations, depending upon the desired mode of application. These formulations may contain as little as about 0.5% to as much as about 95% or more by weight of active ingredient. A herbicidally effective amount depends upon the nature of the seeds or plants to be controlled and the rate of application varies from about 0.01 to approximately 10 pounds per acre, preferably from about 0.02 to about 4 pounds per acre.

Wettable powders are in the form of finely divided particles which disperse readily in water or other dispersants. The wettable powder is ultimately applied to the soil either as a dry dust or as a dispersion in water or other liquid. Typical carriers for wettable powders include fuller's earth, kaolin clays, silicas and other readily wet organic or inorganic diluents. Wettable powders normally are prepared to contain about 5% to about 95% of the active ingredient and usually also contain a small amount of wetting, dispersing, or emulsifying agent to facilitate wetting and dispersion.

Emulsifiable concentrates are homogeneous liquid compositions which are dispersible in water or other dispersant, and may consist entirely of the active compound or salt with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthal, isophorone and other non-volatile organic solvents. For herbicidal application, these concentrates are dispersed in water or other liquid carrier and normally applied as a spray to the area to be treated. The percentage by weight of the essential active ingredient may vary according to the manner in which the composition is to be applied, but in general comprises about 0.5% to 95% of active ingredient by weight of the herbicidal composition.

Granular formulations wherein the toxicant is carried on relatively coarse particles, are usually applied without dilution to the area in which suppression of vegetation is desired. Typical carriers for granular formulations include sand, fuller's earth, attapulgite clay, bentonite clays, montmorillonite clay, vermiculite, perlite and other organic or inorganic materials which absorb or which may be coated with the toxicant. Granular formulations normally are prepared to contain about 0.1% to about 25% of active ingredients which may include surface-active agents such heavy aromatic naphthas, kerosene or other petroleum fractions, or vegetable oils; and/or stickers such as dextrins, glue or synthetic resins.

Typical wetting, dispersing or emulsifing agents and adjuvants used in agricultural formulations include, for example, the alkyl and alkylaryl sulfonates and sulfates and their salts; polyhydric alcohols; polyethoxylated alcohols, esters and fatty amines; and other types of surface-active agents, many of which are available in commerce. The surface-active agent, when used, normally comprises from 0.1% to 30% by weight of the herbicidal composition.

Dusts, which are free-flowing admixtures of the active ingredient with finely divided solids such as talc, clays, flours and other organic and inorganic solids which act as dispersants and carriers for the toxicant, are useful formulations for soil-incorporating application.

Pastes, which are homogeneous suspensions of a finely divided solid toxicant in a liquid carrier such as water or oil, are employed for specific purposes. These formulations normally contain about 5% to about 95% of active ingredients by weight, and may also contain small amounts of a wetting, dispersing or emulsifying agent to facilitate dispersion. For application, the pastes are normally diluted and applied as a spray to the area to be affected.

Other useful formulations for herbicidal applications include simple solutions of the active ingredient in a dispersant in which it is completely soluble at the desired concentration, such as water, acetone, alkylated naphthalenes, xylene and other organic solvents. Pressurized sprays, typically aerosols, wherein the active ingredient is dispersed in finely-divided form as a result of vaporization of a low boiling dispersant solvent carrier, such as the Freons, may also be used.

The phytotoxic compositions of this invention can be applied to the plants in the conventional manner. Thus, the dust and liquid compositions can be applied to the plant by the use of power-dusters, boom and hand sprayers and spray dusters. The compositions can also be applied from airplanes as a dust or a spray or by rope wick applications because they are effective in very low dosages. In order to modify or control growth of germinating seeds or emerging seedlings, as a typical example, the dust and liquid compositions can be applied to the soil according to conventional methods and can be distributed in the soil to a depth of at least 1/2 inch below the soil surface. It is not necessary that the phytotoxic compositions be mechanically admixed with the soil particles since these compositions can also be applied merely by spraying or sprinkling the surface of the soil. The phytotoxic compositions of this invention can also be applied by addition to irrigation water supplied to the field to be treated. This method of application permits the penetration of the compositions into the soil as the water is absorbed therein. Dust compositions, granular compositions or liquid formulations applied to the surface of the soil can be distributed below the surface of the soil by conventional means such as discing, dragging or mixing operations. In the following examples the herbicidal compound can be substituted with the herbicidal salt of the compound.

    ______________________________________                                         EMULSIFIABLE CONCENTRATE FORMULATIONS                                          General Formula with Ranges                                                                     Specific Formula                                              ______________________________________                                         Herbicidal compound                                                                          5-55   herbicidal compound                                                                            24                                        surfactant(s)                                                                                5-25   proprietary blend of oil-                                                                      10                                        solvent(s)   20-90   soluble sulfonates and                                                 100%    polyoxyethylene ethers                                                         polar solvent   27                                                             petroleum hydrocarbon                                                                          39                                                                             100%                                      ______________________________________                                    

    ______________________________________                                         WETTABLE POWDER FORMULATIONS                                                   ______________________________________                                         herbicidal compound                                                                          3-90   herbicidal compound                                                                            80                                        wetting agent                                                                               0.5-2   sodium dialkyl naphtha-                                                                        0.5                                       dispersing agent                                                                            1-8     lene sulfonate                                            diluent(s)   8.5-87  sodium lignosulfonate                                                                          7                                                      100%    attapulgite clay                                                                               12.5                                                                           100%                                      ______________________________________                                    

    ______________________________________                                         EXTRUDED GRANULAR FORMULATIONS                                                 ______________________________________                                         herbicidal compound                                                                          1-20   herbicidal compound                                                                            10                                        binding agent                                                                                0-10   lignin sulfonate                                                                                5                                        diluent(s)   70-99   calcium carbonate                                                                              85                                                     100%                    100%                                      ______________________________________                                    

    ______________________________________                                         FLOWABLE FORMULATIONS                                                          ______________________________________                                         herbicidal compound                                                                         20-70     herbicidal compound                                                                          45                                        surfactant(s)                                                                                1-10     polyoxyethylene                                                                              5                                                                ether                                                   suspending agent(s)                                                                         0.05-1    attagel       0.05                                      antifreeze agent                                                                             1-10     propylene glycol                                                                             10                                        antimicrobial agent                                                                          1-10     1,2-benzisothiazo-                                                                           0.03                                                             line-3-one                                              antifoam agent                                                                              0.1-1     silicone defoamer                                                                            0.02                                      solvent       7.95-77.85                                                                              water         39.9                                                   100%                    100%                                      ______________________________________                                    

When salts are used as the active ingredient in the herbicidal compositions of this invention it is recommended to use salts that are agriculturally acceptable.

The phytotoxic compositions of this invention can also contain other additives, for example, fertilizers, other herbicides and other pesticides, used as adjuvant or in combination with any of the above-described adjuvants. Fertilizers useful in combination with the active ingredients include, for example, ammonium nitrate, urea and superphosphate. 

We claim:
 1. Compound having the structural formula ##STR96## wherein R and R¹ are hydrogen, C₁ -C₄ alkyl, R^(a) OC(O)--, where R^(a) is C₁ -C₄ alkyl;R² is C₁ -C₄ alkoxy; and R³, R⁴ and R⁵ independently are (1) hydrogen; (2) halogen; (3) C₁ -C₄ alkyl; (4) C₁ -C₄ alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁ -C₄ haloalkyl; (9) R^(b) SO_(n) -- wherein R^(b) is C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, phenyl, benzyl, --NR^(d) R^(e) wherein R^(d) and R^(e) independently are hydrogen or C₁ -C₄ alkyl; and n is the integer 0, 1 or 2; ##STR97## wherein R^(c) is C₁ -C₄ alkyl and R^(j) is hydrogen; (11) R^(f) C(O) wherein R^(f) is hydrogen, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy; (12) --NR^(g) R^(h) wherein R^(g) and R^(h) independently are hydrogen or C₁ -C₄ alkyl; or (13) R³ and R⁴ together can form a ring structure with two adjacent carbon atoms of the phenyl ring; and their salts.
 2. The compound of claim 1 wherein R and R¹ are hydrogen or C₁ -C₄ alkyl; R² is C₁ -C₄ alkoxy; R³ and R⁴ independently are hydrogen, halogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, trifluoromethoxy, cyano, nitro, C₁ -C₄ haloalkyl, R^(b) SO_(n) wherein R^(b) is C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, phenyl, benzyl, --NR^(d) R^(e) wherein R^(d) and R^(e) independently are hydrogen and C₁ -C₄ alkyl; and n is the integer 0, 1 or 2; R^(c) C(O)NH-- wherein R^(c) is C₁ -C₄ alkyl; R^(f) C(O)-- wherein R^(f) is hydrogen, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy; or --NR^(g) R^(h) wherein R^(g) and R^(h) independently are hydrogen or C₁ -C₄ alkyl; and R⁵ is hydrogen and their salts.
 3. The compound of claim 1 wherein R and R¹ are hydrogen or C₁ -C₄ alkyl; R² is C₁ -C₄ alkoxy; R³ is hydrogen, halogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, nitro, C₁ -C₄ haloalkyl or R^(b) SO_(n) wherein R^(b) is C₁ -C₄ alkyl and n is the integer 0; R⁴ is hydrogen, halogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, cyano, nitro, C₁ -C₄ haloalkyl or R^(b) SO_(n) wherein R^(b) is C₁ -C₄ alkyl and n is the integer 0, 1 or 2; and R⁵ is hydrogen and their salts.
 4. The compound of claim 1 wherein R and R¹ are hydrogen or methyl; R² is methoxy; R³ is hydrogen, halogen, methyl, C₁ -C₄ alkoxy, nitro, trifluoromethyl or methylthio; R⁴ is hydrogen, halogen, methyl, methoxy, cyano, nitro, trifluoromethyl, methylthio or CH₃ SO₂ ; and R⁵ is hydrogen and their salts.
 5. The compound of claim 3 wherein R³ is in the 3-position and R⁴ is in the 4-position and their salts.
 6. The compound of claim 4 wherein R³ is in the 3-position and R⁴ is in the 4-position and their salts.
 7. The compound of claim 1 wherein R and R¹ are hydrogen or C₁ -C₄ alkyl; R² is C₁ -C₄ alkoxy; R³ is hydrogen, halogen, C₁ -C₄ alkoxy, or R^(b) SO_(n) wherein R^(b) is C₁ -C₄ alkyl and n is the integer 0; R⁴ is R^(b) SO_(n) -- wherein R^(b) is C₁ -C₄ alkyl and n is the integer 2; and R⁵ is hydrogen. 